Efficient methanol-to-hydrogen supply system and control method thereof

Abstract

The invention relates to the field of methanol-to-hydrogen, in particular to an efficient methanol-to-hydrogen supply system and a control method thereof.The efficient methanol-to-hydrogen supply system comprises a methanol water combustion path, a methanol water supply path, an air supply path, a tail gas emission path, a pure hydrogen supply path and a catalytic heating reforming purification integrated device; the air supply path and the methanol water combustion path are communicated with a combustion chamber of the catalytic heating, reforming and purifying integrated device through a tee joint, the methanol water supply path is communicated with a reaction chamber of the catalytic heating, reforming and purifying integrated device, and the pure hydrogen supply path is communicated with a purifying area of the catalytic heating, reforming and purifying integrated device. And the tail gas discharge path is used for discharging tail gas generated after combustion of the methanol water. According to the scheme, stable and reliable pure hydrogen can be provided for a user, the hydrogen supply system is used while being prepared, storage is not needed, catalytic combustion heating is adopted for the whole system, the system is simple, and the comprehensive energy efficiency is higher.

Description

Technical Field

[0001] This invention relates to the field of methanol-to-hydrogen, and more particularly to a high-efficiency methanol-to-hydrogen supply system and its control method. Background Technology

[0002] Currently, hydrogen energy, as a clean, efficient, safe, and sustainable new energy source, is considered the most promising clean energy source of the 21st century and a strategic energy development direction for humanity, attracting widespread attention and in-depth research from countries around the world. Intense competition has emerged among nations in the commercialization of hydrogen energy. Due to the physical properties of hydrogen, its storage and transportation require high-pressure containers, posing significant potential safety risks. It is precisely these potential safety risks that have severely hindered the commercialization of hydrogen energy.

[0003] To address the issues of hydrogen storage and transportation, current solutions primarily employ on-site hydrogen production, producing hydrogen only when needed. Currently, the mainstream hydrogen production method is methanol reforming. This invention provides an efficient methanol-to-hydrogen supply system and control method based on high-temperature methanol reforming, achieving self-heating of methanol, reforming to produce hydrogen, purification, and a safe and stable hydrogen supply. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide an efficient methanol-to-hydrogen supply system to solve the problem of hydrogen supply.

[0005] The technical solution of the present invention to solve the above-mentioned technical problems is as follows: A high-efficiency methanol-to-hydrogen supply system includes a methanol-water combustion circuit, a methanol-water supply circuit, an air supply circuit, a tail gas emission circuit, a pure hydrogen supply circuit, and a catalytic heating reforming purification integrated device. The air supply circuit and the methanol-water combustion circuit are connected to the combustion chamber of the catalytic heating reforming purification integrated device through a three-way valve. The methanol-water supply circuit is connected to the reaction chamber of the catalytic heating reforming purification integrated device. The pure hydrogen supply circuit is connected to the purification zone of the catalytic heating reforming purification integrated device. The tail gas emission circuit is used to discharge the tail gas after methanol-water combustion.

[0006] Furthermore, it also includes an unrecovered hydrogen path, one end of which is connected to the purification zone of the integrated catalytic heating reforming and purification device, and the other end of which is connected to a pipeline that connects the methanol-water combustion path and the integrated catalytic heating reforming and purification device.

[0007] Furthermore, it also includes a primary preheater and a secondary preheater. The pure hydrogen supply line and the methanol-water supply line are connected by heat exchange through the primary preheater, and the unrecovered hydrogen line and the methanol-water supply line are connected by heat exchange through the secondary preheater.

[0008] Furthermore, the air supply path and the exhaust gas emission path are connected by a heat exchanger for heat exchange.

[0009] Furthermore, the methanol-water combustion circuit includes a methanol-water combustion pump, a first flow meter, a first solenoid valve, and a heater connected in sequence via pipelines, with the heater connected to the three-way pipeline.

[0010] Furthermore, the methanol-water supply path includes a reformed methanol-water pump, a one-way valve, and a second pressure sensor connected in sequence via pipelines. The second pressure sensor is connected to the purification zone pipeline of the integrated catalytic heating reforming and purification device.

[0011] Furthermore, the air supply path includes a combustion fan, a filter, and a second flow meter arranged in sequence via pipelines, with the second flow meter connected to the three-way pipeline.

[0012] Furthermore, the pure hydrogen supply path includes a second solenoid valve, a safety valve, and a pressure reducing valve connected in sequence via pipelines, and the second solenoid valve is connected to the purification zone of the integrated catalytic heating reforming purification device.

[0013] This invention provides a high-efficiency methanol-to-hydrogen supply system, comprising a methanol-water combustion circuit, a methanol-water supply circuit, an air supply circuit, a tail gas emission circuit, a pure hydrogen supply circuit, and a catalytic heating reforming purification integrated device. The air supply circuit and the methanol-water combustion circuit are connected to the combustion chamber of the catalytic heating reforming purification integrated device via a three-way valve. The methanol-water supply circuit is connected to the reaction chamber of the catalytic heating reforming purification integrated device. The pure hydrogen supply circuit is connected to the purification zone of the catalytic heating reforming purification integrated device. The tail gas emission circuit is used to discharge the tail gas after methanol-water combustion. In this way, the methanol-water combustion circuit provides heat to the methanol-water supply circuit by burning methanol, raising the temperature of the methanol-water in the methanol-water supply circuit to facilitate the catalytic reaction. The air supply circuit ensures the oxygen supply to the combustion chamber of the methanol-water combustion circuit, and the pure hydrogen supply circuit supplies the hydrogen generated after the reaction to the application unit. The tail gas emission circuit discharges the waste gas after combustion in the methanol-water combustion circuit. This solution can provide users with stable and reliable pure hydrogen, and the hydrogen supply system is on-demand, requiring no storage. Overall, the system uses catalytic combustion heating, is simple, and has a higher overall energy efficiency.

[0014] This invention provides a control method for a high-efficiency methanol-to-hydrogen supply system, comprising the following steps:

[0015] S1. Set the vaporization temperature and turn on the methanol-water heater;

[0016] Set the budget flow rate and turn on the combustion fan at the same time;

[0017] S2. When the vaporization temperature is reached, turn on the methanol combustion water pump to the preset flow rate;

[0018] S3. When the combustion chamber temperature is collected and the catalytic combustion status is normal, wait for the system to heat up.

[0019] S4. Once the reforming temperature reaches the reaction temperature, turn on the reforming methanol water pump.

[0020] S5. Adjust the reforming reaction pressure and control the start and stop of the reforming methanol water pump by collecting the pressure of the reforming methanol water circuit.

[0021] Thus, when the system starts, the methanol-water heater is first turned on, the vaporization temperature is set, and the combustion blower is simultaneously turned on, with the preset flow rate set. When the set vaporization temperature is reached, the methanol-water combustion pump is turned on to the preset flow rate. The catalytic combustion status is determined by T2. When catalytic combustion is in a normal state, the system waits for heating. When the reforming temperature T3 reaches the reaction temperature, the reforming methanol-water pump is turned on, and the reforming reaction pressure is adjusted by a regulating valve. The start and stop of the reforming methanol-water pump are controlled by feedback from a second pressure sensor. The catalytic combustion temperature is controlled by adjusting the flow rates of the methanol-water combustion pump and the combustion blower. The hydrogen supply pipeline is regulated by a safety valve and a pressure reducing valve. Attached Figure Description

[0022] Figure 1 This is a system schematic diagram of a high-efficiency methanol-to-hydrogen supply system according to the present invention;

[0023] Figure 2 This is a schematic diagram of the integrated catalytic heating reforming and purification device of a high-efficiency methanol-to-hydrogen supply system according to the present invention.

[0024] The attached diagram lists the components represented by each number as follows:

[0025] 1. Methanol-water combustion circuit, 101. Methanol-water combustion pump, 102. First flow meter, 103. First solenoid valve, 104. Heater; 2. Methanol-water supply circuit, 201. Reforming methanol-water pump, 202. Check valve, 203. Second pressure sensor; 3. Air supply circuit, 301. Combustion fan, 302. Filter, 303. Second flow meter; 4. Exhaust gas emission circuit; 5. Pure hydrogen supply circuit, 501. Second solenoid valve, 502. Safety valve, 503. Pressure reducing valve; 6. Catalytic heating reforming and purification integrated unit; 7. Unrecovered hydrogen circuit; 8. First-stage preheater; 9. Second-stage preheater; 10. Heat exchanger. Detailed Implementation

[0026] The principles and features of the present invention are described below with reference to the accompanying drawings. The examples given are only for explaining the present invention and are not intended to limit the scope of the present invention.

[0027] In the description of this invention, it should be understood that the terms "upper", "lower", "center", "inner", "outer", "top", "bottom", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention.

[0028] In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "linking" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0029] like Figure 1 As shown, the present invention provides a high-efficiency methanol-to-hydrogen supply system, including a methanol-water combustion path 1, a methanol-water supply path 2, an air supply path 3, a tail gas emission path 4, a pure hydrogen supply path 5, and a catalytic heating reforming purification integrated device 6. The air supply path 3 and the methanol-water combustion path 1 are connected to the combustion chamber of the catalytic heating reforming purification integrated device 6 via a three-way valve. The methanol-water supply path 2 is connected to the reaction chamber of the catalytic heating reforming purification integrated device 6. The pure hydrogen supply path 5 is connected to the purification zone of the catalytic heating reforming purification integrated device 6. The tail gas emission path 4 is used to discharge the tail gas after the methanol-water combustion. In this way, methanol-water combustion circuit 1 provides heat to methanol-water supply circuit 2 by burning methanol, raising the temperature of the methanol-water in methanol-water supply circuit 2 to facilitate the catalytic reaction. Air supply circuit 3 ensures the oxygen supply to the combustion chamber of methanol-water combustion circuit 1, pure hydrogen supply circuit 5 supplies the hydrogen generated after the reaction to the application unit, and exhaust gas discharge circuit 4 discharges the exhaust gas after combustion in methanol-water combustion circuit 1. This solution can provide users with stable and reliable pure hydrogen, and the hydrogen supply system is produced and used on demand without storage. Overall, the system adopts catalytic combustion heating, which is simple and has a higher comprehensive energy efficiency.

[0030] The efficient methanol-to-hydrogen supply system of the present invention, such as Figure 1As shown, based on the previously described technical solution, it can also include an unrecovered hydrogen path 7. One end of the unrecovered hydrogen path 7 is connected to the purification zone of the integrated catalytic heating reforming and purification device 6, and the other end of the unrecovered hydrogen path 7 is connected to the pipeline connecting the methanol-water combustion path 1 and the integrated catalytic heating reforming and purification device 6. In this way, by setting up the unrecovered hydrogen path 7, the unused hydrogen in the purification zone of the integrated catalytic heating reforming and purification device 6 is transported to the combustion chamber for secondary utilization, thereby ensuring full utilization of energy.

[0031] The efficient methanol-to-hydrogen supply system of the present invention, such as Figure 1 As shown, based on the previously described technical solution, it can also include a primary preheater 8 and a secondary preheater 9. The pure hydrogen supply line 5 and the methanol-water supply line 2 are connected by heat exchange through the primary preheater 8, and the unrecovered hydrogen line 7 and the methanol-water supply line 2 are connected by heat exchange through the secondary preheater 9. During the entire hydrogen production process, the hydrogen generated by the methanol-water reaction has a high temperature, making direct use inconvenient. Simply cooling it would increase the system's complexity and waste its high temperature. This solution employs a two-stage preheating process. The pure hydrogen supply line 5 and the methanol-water supply line 2 are connected by heat exchange through the primary preheater 8, transferring the heat of the hydrogen in the pure hydrogen supply line 5 to the methanol-water supply line 2 to heat the methanol-water undergoing the catalytic reaction, thereby improving the reaction efficiency between the methanol-water and the catalyst. Simultaneously, the unrecovered hydrogen line 7 and the methanol-water supply line 2 are connected by heat exchange through the secondary preheater 9, further heating the methanol-water in the methanol-water supply line 2.

[0032] The efficient methanol-to-hydrogen supply system of the present invention, such as Figure 1 As shown, based on the previously described technical solution, the air supply path 3 and the exhaust path 4 can also be connected by a heat exchanger 10. In this way, since the exhaust gas is a product of the combustion of methanol and water in the combustion chamber, and its temperature is relatively high, direct discharge would be wasteful. Therefore, this solution utilizes the heat of the exhaust gas to heat the air supply path 3.

[0033] This application also provides a control method for a high-efficiency methanol-to-hydrogen supply system, comprising the following steps:

[0034] S1. Set the vaporization temperature and turn on the methanol-water heater 104.

[0035] Set the budget flow rate and turn on the combustion fan 301 simultaneously;

[0036] S2. When the vaporization temperature is reached, start the combustion methanol water pump 101 to the preset flow rate;

[0037] S3. When the combustion chamber temperature is collected and the catalytic combustion status is normal, wait for the system to heat up.

[0038] S4. When the reforming temperature reaches the reaction temperature, start the reforming methanol water pump 201.

[0039] S5. Adjust the reforming reaction pressure and control the start and stop of the reforming methanol water pump 201 by collecting the reforming methanol water circuit pressure.

[0040] When the system starts, the methanol-water heater 104 is first turned on, the vaporization temperature is set, and the combustion blower 301 is turned on, with the preset flow rate set. When the set vaporization temperature is reached, the combustion methanol-water pump 101 is turned on to the preset flow rate. The catalytic combustion status is determined by T2. When the catalytic combustion is in a normal state, the system waits for the temperature to rise. When the reforming temperature T3 reaches the reaction temperature, the reforming methanol-water pump 201 is turned on, the reforming reaction pressure is adjusted by the regulating valve, and the start and stop of the reforming methanol-water pump 201 is controlled by the pressure sensor feedback of the second pressure sensor 203. The catalytic combustion temperature is controlled by adjusting the flow rates of the combustion methanol-water pump 101 and the combustion blower 301. The hydrogen supply pipeline is regulated by the safety valve 502 and the pressure reducing valve 503.

[0041] Example

[0042] like Figure 1 As shown, this system provides safe, reliable, and stable hydrogen through an integrated methanol catalyst combustion heating reforming hydrogen production and purification unit.

[0043] When the system starts, heater 104 is turned on to burn methanol-water vaporization. When the vaporization temperature is reached, methanol-water combustion pump 101 is turned on, and the flow rate of methanol-water combustion is recorded by the first flow meter 102. The flow rate of combustion fan 301 is calculated based on the air-fuel ratio, and combustion fan 301 is turned on. The flow feedback control of combustion fan 301 parameters is achieved through the second flow meter 303, ultimately realizing air flow control. The catalytic combustion state is determined based on the temperature rise at T2. The high-temperature exhaust gas after catalytic combustion preheats the combustion air through heat exchanger 10. The preheated air then enters the integrated device for catalytic combustion and heat release.

[0044] When the catalytic combustion is in operation, the system waits for further heating. T3 is the reforming temperature control point. After the reforming temperature reaches the operating temperature, the reforming methanol water pump 201 is turned on. The reforming temperature is maintained within the set range by adjusting the flow rate of the combustion methanol water and the flow rate of the combustion fan 301. The reformed methanol water and high-temperature pure hydrogen undergo primary heat exchange through the primary preheater 8, and undergo secondary heat exchange with unrecovered high-temperature hydrogen through the secondary preheater 9. After the secondary heat exchange, the methanol water enters the superheater in the integrated catalyst heating, reforming, and purification unit for heating. After heating, it enters the reforming unit to produce hydrogen-rich gas. The outlet of the reforming unit is connected to the inlet of the purification unit, and the hydrogen-rich gas enters the purification unit to purify the hydrogen. The unrecovered hydrogen enters the catalytic combustion chamber for combustion after secondary heat exchange. As the unrecovered hydrogen enters the catalytic combustion unit, the catalytic combustion temperature rises significantly. At this point, the flow rate of the combustion methanol water is gradually reduced, and the fan flow rate is adjusted to stabilize the combustion temperature.

[0045] The purified hydrogen is output through the pure hydrogen outlet of the purification unit. A safety valve 502 is installed in the purified hydrogen pipeline to stabilize the hydrogen supply pressure. When the demand is low, excess hydrogen is discharged through the safety valve 502 to stabilize the hydrogen supply in the pipeline.

[0046] The reformed gas outlet is connected to the purification inlet. The pressure of the unrecovered hydrogen outlet controls the on / off state and feed rate of the reformed methanol water pump 201. Hydrogen flows into the end-use terminal after passing through a buffer damping device and a pressure reducing valve 503. The first pressure sensor is used to detect the pure hydrogen pipeline pressure, T1 is used to detect the pure hydrogen outlet temperature, and T4 is used to detect the hydrogen temperature after the first-stage heat exchange.

[0047] like Figure 2 As shown, a catalytic combustion chamber is located at the lower end of the integrated unit. From bottom to top, the catalytic combustion chamber includes an air inlet, a methanol-water vaporization inlet, a recovered hydrogen inlet, a gas distributor, and the catalytic combustion catalyst. During catalytic combustion heating, air carrying a large amount of heat enters the catalytic combustion exhaust chamber. The catalytic combustion exhaust chamber is composed of an annular closed reforming chamber and an outer shell, forming an inner and outer exhaust chamber that are interconnected. The inner chamber is the inner ring chamber of the annular closed reformer, and the outer chamber consists of the outer ring of the annular closed reformer and the outer shell. The high-temperature gas from catalytic combustion flows from the high-temperature zone of the inner chamber into the outer chamber and finally exits from the lower end of the integrated unit.

[0048] Catalytic combustion consists of two stages: a start-up stage and a normal operation stage. During the start-up stage, the methanol-water mixture needs to be heated and vaporized to initiate catalytic combustion. Once the catalytic combustion is operating normally, a vaporization coil located on the outer wall of the device assists in the vaporization of the methanol-water mixture. When the entire system is operating normally, purified but unrecovered hydrogen enters the catalytic combustion chamber through a designated channel for heating, providing a heat source for the entire system. During this time, the amount of methanol-water mixture used gradually decreases until the supply stops.

[0049] The hydrogen purification unit is located in the center of the catalytic combustion exhaust chamber. A reformed methanol-water vaporization coil is installed on the inner wall of the exhaust chamber for the vaporization of reformed methanol-water. One end of the reformed methanol-water vaporization coil is connected to the reformer inlet, and the other end is connected to heat exchanger 10, pressure sensor, check valve, and high-pressure pump.

[0050] The reformer outlet is connected to the inlet of the hydrogen purification unit. The recovery outlet of the purification unit is connected to the heat exchanger 10, temperature sensor, solenoid valve, safety valve 502, and pressure reducing valve 503. The end of the pressure reducing valve 503 is for terminal use. The unrecovered hydrogen outlet of the purification unit is connected to the heat exchanger 10, pressure sensor, regulating valve, heater 104, and unrecovered hydrogen interface of the catalytic combustion unit.

[0051] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A high-efficiency methanol-to-hydrogen supply system, characterized in that: It includes a methanol-water combustion path (1), a methanol-water supply path (2), an air supply path (3), a tail gas emission path (4), a pure hydrogen supply path (5), and a catalytic heating reforming purification integrated device (6). The air supply path (3) and the methanol-water combustion path (1) are connected to the combustion chamber of the catalytic heating reforming purification integrated device (6) through a three-way valve. The methanol-water supply path (2) is connected to the reaction chamber of the catalytic heating reforming purification integrated device (6). The pure hydrogen supply path (5) is connected to the purification zone of the catalytic heating reforming purification integrated device (6). The tail gas emission path (4) is used to discharge the tail gas after the methanol-water combustion.

2. The high-efficiency methanol-to-hydrogen supply system according to claim 1, characterized in that: It also includes an unrecovered hydrogen path (7), one end of which is connected to the purification zone of the integrated catalytic heating reforming and purification device (6), and the other end of which is connected to the pipeline connecting the methanol-water combustion path (1) and the integrated catalytic heating reforming and purification device (6).

3. The high-efficiency methanol-to-hydrogen supply system according to claim 2, characterized in that: It also includes a primary preheater (8) and a secondary preheater (9). The pure hydrogen supply line (5) and the methanol-water supply line (2) are connected by heat exchange through the primary preheater (8), and the unrecovered hydrogen line (7) and the methanol-water supply line (2) are connected by heat exchange through the secondary preheater (9).

4. The high-efficiency methanol-to-hydrogen supply system according to claim 3, characterized in that: The air supply path (3) and the exhaust path (4) are connected by a heat exchanger (10).

5. The high-efficiency methanol-to-hydrogen supply system according to claim 1, characterized in that: The methanol-water combustion circuit (1) includes a methanol-water combustion pump (101), a first flow meter (102), a first solenoid valve (103), and a heater (104) connected in sequence by pipelines. The heater (104) is connected to the three-way pipeline.

6. The high-efficiency methanol-to-hydrogen supply system according to claim 1, characterized in that: The methanol-water supply path (2) includes a reformed methanol-water pump (201), a one-way valve (202), and a second pressure sensor (203) connected in sequence via pipelines. The second pressure sensor (203) is connected to the purification zone pipeline of the integrated catalytic heating reforming and purification device (6).

7. The high-efficiency methanol-to-hydrogen supply system according to claim 1, characterized in that: The air supply path (3) includes a combustion fan (301), a filter (302), and a second flow meter (303) connected in sequence by pipes. The second flow meter (303) is connected to the three-way pipe.

8. The high-efficiency methanol-to-hydrogen supply system according to claim 1, characterized in that: The pure hydrogen supply path (5) includes a second solenoid valve (501), a safety valve (502) and a pressure reducing valve (503) connected in sequence by pipelines. The second solenoid valve (501) is connected to the purification zone of the integrated catalytic heating reforming purification device (6).

9. A control method for a high-efficiency methanol-to-hydrogen supply system, characterized in that: Includes the following steps: S1. Set the vaporization temperature and turn on the methanol-water heater (104); Set the budget flow rate and turn on the combustion fan (301); S2. When the vaporization temperature is reached, turn on the methanol combustion water pump (101) to the preset flow rate; S3. When the combustion chamber temperature is collected and the catalytic combustion status is normal, wait for the system to heat up. S4. When the reforming temperature reaches the reaction temperature, turn on the reforming methanol water pump (201). S5. Adjust the reforming reaction pressure and control the start and stop of the reforming methanol water pump (201) by collecting the reforming methanol water circuit pressure.

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