A high-efficiency methanol reforming hydrogen production device

Abstract

The invention discloses a high-efficiency methanol reforming hydrogen production device, comprising a shell, a reactor, a heat exchanger, a liquid supply pipe and an exhaust pipe. The shell comprises an outer shell and an inner shell arranged in the outer shell, a vacuum interlayer is arranged between the inner shell and the outer shell, the reactor is arranged in the inner shell, the heat exchanger is arranged at the front end of the shell, the heat exchanger is filled with a heat exchange medium, one end of the liquid supply pipe is connected to the liquid inlet of the reactor, the other end of the liquid supply pipe is exposed after passing through the heat exchanger, one end of the exhaust pipe is connected to the gas outlet of the reactor, and the other end of the exhaust pipe is exposed after passing through the heat exchanger. On the one hand, the reactor is arranged in the shell with a vacuum interlayer, which reduces the heat energy loss of the reactor; on the other hand, the hydrogen and carbon dioxide after the reaction have a very high temperature (have residual heat energy), and the heat energy is transferred to the methanol water in the liquid supply pipe through the heat exchanger, so that the temperature of the methanol water is increased, that is, the residual heat is recovered; energy saving is achieved from these two aspects.

Description

Technical Field

[0001] The invention relates to the technical field of methanol hydrogen production, and in particular to a high-efficiency methanol reforming hydrogen production device. Background Art

[0002] Methanol has a high mass hydrogen storage density, which is the bottleneck problem in solving the storage and transportation of hydrogen energy applications. Generally speaking, there are three methods for producing hydrogen from methanol: methanol steam reforming (SRM), methanol oxidation reforming (OMR) and methanol partial oxidation (POM). Among them, methanol steam reforming (SRM) technology is more mature, with a hydrogen production rate of up to 75%. However, the current methanol steam reforming (SRM) device is large in size, takes time to start, and is more energy-consuming, so it has not been widely used in mobile vehicles. The methanol steam reforming hydrogen production process is a thermodynamically favorable endothermic reaction with a high temperature. The operating temperature is 250°C, so a lot of energy will be consumed during heating, and continuous heating is still required during the reaction process; when the demand for hydrogen supply increases, the device volume increases, and the energy required for heating also increases accordingly. The heating method for partial methanol steam reforming is to burn methanol for heating. This method is more difficult to control the temperature, and the consumption of methanol reduces the hydrogen production rate. The relatively high operating temperature and the presence of the vaporization unit cause the distributed methanol hydrogen production system to respond slowly under startup conditions. Summary of the invention

[0003] To this end, the present invention provides a high-efficiency methanol reforming hydrogen production device to solve the above-mentioned technical problems.

[0004] In order to achieve the above object, the present invention provides the following technical solutions:

[0005] A high-efficiency methanol reforming hydrogen production device comprises a shell, a reactor, a heat exchanger, a liquid supply pipe and an exhaust pipe, wherein the shell comprises an outer shell and an inner shell arranged in the outer shell, a vacuum interlayer is arranged between the inner shell and the outer shell, the reactor is arranged in the inner shell, the heat exchanger is arranged at the front end of the shell, the heat exchanger is filled with a heat exchange medium, one end of the liquid supply pipe is connected to the liquid inlet of the reactor, the other end of the liquid supply pipe passes through the heat exchanger and is exposed, one end of the exhaust pipe is connected to the gas outlet of the reactor, and the other end of the exhaust pipe passes through the heat exchanger and is exposed.

[0006] Furthermore, the reactor includes an inner core, an outer core, a separator tube and a ceramic heating plate. The separator tube is arranged along the front-to-back direction. The separator tube separates the inner core and the outer core on the circumferential side and the rear of the inner core is connected to the outer core. The separator tube is made of corrosion-resistant metal, and the ceramic heating plate is arranged on the circumferential side of the separator tube.

[0007] Furthermore, the ceramic heating plate is in a strip shape and is arranged along the front-to-back direction; a plurality of the ceramic heating plates are provided, and the plurality of the ceramic heating plates are evenly distributed around the circumference of the separation cylinder.

[0008] Furthermore, a first type of catalyst having high catalytic activity for methanol at low temperatures is placed at the front of the inner core, a second type of catalyst having high catalytic activity for methanol at high temperatures is placed at the rear of the inner core and the outer core, and a third type of catalyst having high activity for carbon monoxide is placed at the front of the outer core.

[0009] Furthermore, the reactor further comprises a nozzle, which is arranged at the front end of the inner core and is connected to the liquid supply pipe.

[0010] Furthermore, the reactor also includes a thermometer, which is arranged at the front part of the inner core.

[0011] Furthermore, the portion of the liquid supply pipe located in the heat exchanger is distributed in a spiral shape.

[0012] Furthermore, the portion of the exhaust pipe located in the heat exchanger is distributed in a spiral shape.

[0013] Furthermore, the heat exchange medium is heat transfer oil.

[0014] Furthermore, the high-efficiency methanol reforming hydrogen production device also includes a controller, the liquid inlet of the liquid supply pipe is connected to the methanol water raw material pump, the gas outlet of the exhaust pipe is connected to the gas flow meter, the controller is electrically connected to the methanol water raw material pump, the gas flow meter, the ceramic heating plate and the thermometer, and the controller controls the working status of the methanol water raw material pump and the ceramic heating plate based on feedback information from the gas flow meter and the thermometer.

[0015] The present invention has the following advantages:

[0016] 1. Energy saving: On the one hand, the reactor is set in a shell with a vacuum interlayer to reduce the heat energy loss of the reactor; on the other hand, the hydrogen and carbon dioxide after the reaction have a very high temperature (have waste heat energy), and the heat energy is transferred to the methanol water in the liquid supply pipe through the heat exchanger to increase the temperature of the methanol water, that is, to recover the waste heat; energy saving is achieved from these two aspects.

[0017] 2. Fast start-up: By setting a ceramic heating plate outside the separation cylinder, electric heating is used to replace the existing methanol combustion heating, which heats up faster, so the start-up time is shorter and the start-up is faster.

[0018] 3. Intelligent control: Based on the feedback temperature information, the controller controls the feeding time and feeding amount of the methanol water raw material pump to ensure a stable balance between the heat absorption and heating in the reactor, and adjusts the switch of the ceramic heating plate to stabilize the temperature in the reactor; based on the feedback flow information and the required gas output, the controller controls the feeding time and feeding amount of the methanol water raw material pump, and adjusts the switch of the ceramic heating plate to maintain the required gas output. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to more clearly illustrate the implementation methods of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for the implementation methods or the description of the prior art. Obviously, the drawings in the following description are only exemplary, and for ordinary technicians in this field, other implementation drawings can be derived from the provided drawings without creative work.

[0020] The structures, proportions, sizes, etc. illustrated in this specification are only used to match the contents disclosed in the specification so as to facilitate understanding and reading by persons familiar with the technology. They are not used to limit the conditions under which the present invention can be implemented, and therefore have no substantial technical significance. Any structural modification, change in proportion or adjustment of size shall still fall within the scope of the technical contents disclosed in the present invention without affecting the effects and purposes that can be achieved by the present invention.

[0021] Figure 1 A schematic structural diagram of a high-efficiency methanol reforming hydrogen production device provided in an embodiment of the present invention;

[0022] Figure 2 A cross-sectional view of a high-efficiency methanol reforming hydrogen production device provided in an embodiment of the present invention;

[0023] Figure 3 A cross-sectional view of a high-efficiency methanol reforming hydrogen production device provided in an embodiment of the present invention;

[0024] Figure 4 This is a working principle diagram of a high-efficiency methanol reforming hydrogen production device provided in an embodiment of the present invention.

[0025] In the figure: 1-outer shell, 2-inner shell, 3-controller, 4-vacuum interlayer, 5-reactor, 6-heat exchanger, 7-nozzle, 8-inner core, 9-outer core, 10-thermometer, 11-separation tube, 12-ceramic heating plate, 13-first type catalyst, 14-second type catalyst, 15-third type catalyst, 16-liquid supply pipe, 16a-liquid inlet, 16b-liquid outlet, 17a-air inlet, 17b-air outlet. DETAILED DESCRIPTION

[0026] The following is a description of the implementation of the present invention by specific embodiments. People familiar with the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] The terms such as "upper", "lower", "left", "right", "middle", etc. cited in this specification are only for the convenience of description and are not intended to limit the scope of implementation of the present invention. Changes or adjustments to their relative relationships should be regarded as within the scope of implementation of the present invention without substantially changing the technical content.

[0028] like Figures 1 to 4As shown, this embodiment provides a high-efficiency methanol reforming hydrogen production device, including a shell, a reactor 5, a heat exchanger 6, a liquid supply pipe 16 and an exhaust pipe. The shell is a cylindrical shell with an open front end and closed other parts, including an outer shell 1 and an inner shell 2 arranged in the outer shell 1, and a vacuum interlayer 4 is provided between the inner shell 2 and the outer shell 1. The reactor 5 is arranged in the inner shell 2, and the reactor 5 is used to convert the methanol water sent by the liquid supply pipe 16 into hydrogen and carbon dioxide under the action of a catalyst. In this process, the reactor 5 has a high temperature (generally at 250°C), so the exhausted gas also has a high temperature property. The heat exchanger 6 is arranged in the front end opening of the shell, and the heat exchanger 6 is filled with a heat exchange medium. The liquid outlet 16b of the liquid supply pipe 16 is connected to the liquid inlet of the reactor 5, and the liquid inlet 16a of the liquid supply pipe 16 passes through the heat exchanger 6 and is exposed from the front end of the heat exchanger 6. The exposed liquid inlet 16a is connected to the methanol water raw material pump. The air inlet 17a of the exhaust pipe is connected to the gas outlet of the reactor 5, and the air outlet 17b of the exhaust pipe passes through the heat exchanger 6 and is exposed from the front end of the heat exchanger 6. The exposed air outlet 17b is connected in series with a gas flow meter. In this embodiment, multiple exhaust pipes are provided, and the air outlets 17b of multiple exhaust pipes are collected and then connected to the gas flow meter. It should be pointed out that the exhaust pipe can be continuous (meaning that the gas cannot directly contact the heat exchange medium) or intermittent (meaning that the gas can directly contact the heat exchange medium) in the heat exchanger 6. On the one hand, the reactor 5 is arranged in a shell with a vacuum interlayer 4, which reduces the heat energy loss of the reactor 5; on the other hand, the hydrogen and carbon dioxide after the reaction have a very high temperature (have waste heat energy), and the heat energy is transferred to the methanol water in the liquid supply pipe 16 through the heat exchanger 6, so that the temperature of the methanol water is increased, that is, the waste heat is recovered; energy saving is achieved from these two aspects. When the device is in operation, methanol water enters the reactor 5, and the heat exchanger 6 can heat the methanol water to a temperature close to 180°C, so that the reactor 5 will not be greatly cooled down due to the low temperature of the feed (the normal operating temperature of the reactor 5 is 250°C). The thermal reaction part (reactor 5) and the heat recovery part (heat exchanger 6) involved in the entire device are operated under a vacuum environment, so the endothermic reaction of methanol reforming can be completed with low energy consumption.

[0029] The reactor 5 includes an inner core 8, an outer core 9, a nozzle 7, a separation tube 11, a ceramic heating plate 12 and a thermometer 10. The outer core 9 wraps the inner core 8; the separation tube 11 is arranged in the front-to-back direction, and the separation tube 11 separates the inner core 8 and the outer core 9 on the circumferential side, and the rear of the inner core 8 is connected to the outer core 9. The nozzle 7 is arranged at the front end of the inner core 8, and the nozzle 7 is connected to the liquid outlet 16b of the liquid supply pipe 16. Methanol water will be sprayed out from the nozzle 7 at the front end of the inner core 8. Due to the high temperature and high injection pressure, the sprayed methanol water has been completely vaporized to form gaseous methanol water. Because the temperature of methanol water is relatively low (referring to 180°C lower than 250°C), it needs to continue to absorb heat, so the temperature of the front part of the inner core 8 will be reduced. Therefore, a first type catalyst 13 with high catalytic activity for methanol at low temperature is placed at the front part of the inner core 8 to improve the catalytic effect and high hydrogen production rate. After the methanol water absorbs heat, the temperature rises to the ideal temperature (250°C). At this time, the heated methanol water comes to the rear of the inner core 8. Therefore, the second type catalyst 14 with high catalytic activity to methanol at high temperature is placed at the rear of the inner core 8 and the outer core 9 to improve the catalytic effect and high hydrogen production rate; the front of the outer core 9 is the part connected to the exhaust pipe, and the gas gathers at this part. The gas contains not only hydrogen and carbon dioxide, but also a small amount of carbon monoxide. Therefore, the third type catalyst 15 with high activity to carbon monoxide is placed at the front of the outer core 9 to reduce the content of carbon monoxide. The vaporized methanol water will first pass through the catalyst of the inner core 8 to the channel behind the inner core 8 to the rear of the outer core 9, and then pass through the catalyst of the outer core 9 to the front of the outer core 9; such a design increases the time that the methanol water contacts the catalyst, making the methanol reforming reaction more effective. The ceramic heating plate 12 is arranged on the peripheral side of the separation cylinder 11, and the separation cylinder 11 is made of corrosion-resistant metal. After the ceramic heating plate 12 is powered on and heated, both the inner core 8 and the outer core 9 can be heated. The ceramic heating plate 12 is in a strip shape and is arranged in the front-to-back direction; there are multiple ceramic heating plates 12, and the multiple ceramic heating plates 12 are evenly distributed on the peripheral side of the separation cylinder 11; so that the catalysts of the inner core 8 and the outer core 9 can be evenly heated, and the temperature of the methanol reforming reaction can be accurately maintained. By arranging the ceramic heating plate 12 outside the separation cylinder 11, the electric heating method is used to replace the existing combustion methanol heating, and the temperature rises faster, so the startup time is shorter and the startup is faster. Generally, the power line of the ceramic heating plate 12 is wired in the power supply tube that runs through the heat exchanger 6, and the power line is connected to the controller 3, so that the ceramic heating plate 12 works under the control of the controller 3. The thermometer 10 is arranged in the front part of the inner core 8 for real-time measurement of the temperature of the reactor 5. In this embodiment, the liquid supply pipe 16, the exhaust pipe and the power supply pipe are all made of high temperature resistant materials.

[0030] Three types of catalysts with different characteristics are used in the reactor 5 to match the reaction process of gasified methanol water at different stages. Starting from the front end of the inner core 8, when the gasified methanol water enters the reactor 5, the temperature is relatively low, about 180°C, so an appropriate amount of low-temperature and high-activity first-type catalyst 13 is placed at the front end of the inner core 8. The cost of this catalyst is relatively high, so using it in moderation can reduce waste and improve cost-effectiveness; at this stage or position, part of the methanol water that has not been heated up is first reformed. When the system starts to operate, a heating device, i.e., a ceramic heating plate 12, must be used to heat it to the ideal temperature for the methanol reforming reaction. The low-temperature and high-activity catalyst shortens the time for the methanol reforming reaction to start, making full use of the time before the hydrogen-rich gas is output. When a part of the gasified methanol water is reforming, the unreformed methanol water will increase its temperature to the most effective reforming temperature (about 250°C); therefore, most of the catalysts in the inner and outer cores 9 are second-type catalysts 14 with higher temperatures but better activity, so that all the methanol water entering the reactor 5 can be catalyzed and reformed to become hydrogen-rich gas. During the catalytic process, a small amount of carbon monoxide will be generated because a proper amount of third type catalyst 15 active to carbon monoxide is placed at the front end of the outer core 9 near the exhaust pipe to remove the carbon monoxide in the hydrogen-rich gas.

[0031] Optionally, the portion of the liquid supply pipe 16 located in the heat exchanger 6 is distributed in a spiral shape, so that the heat exchange area with the heat exchange medium can be increased, which is beneficial to the improvement of the waste heat utilization rate. Optionally, the portion of the exhaust pipe located in the heat exchanger 6 is distributed in a spiral shape, so that the heat exchange area with the heat exchange medium can be increased, which is beneficial to the improvement of the waste heat utilization rate. Optionally, the exhaust pipe disappears after entering the heat exchanger 6, that is, the exhaust pipe is very short, and the gas is allowed to flow in the heat exchanger 6, allowing the gas to directly contact the heat exchange medium, so that the heat exchange efficiency is higher; accordingly, a shorter exhaust pipe is also provided at the front end of the heat exchanger 6 to connect a gas flow meter, a hydrogen storage device or a hydrogen use device. Optionally, the heat exchange medium is heat transfer oil. The above optional implementation scheme is only for example and does not limit the implementation of other alternative technical solutions.

[0032] In this embodiment, the high-efficiency methanol reforming hydrogen production device also includes a controller 3, the liquid inlet 16a of the liquid supply pipe 16 is connected to the methanol water raw material pump, the gas outlet of the exhaust pipe is connected to the gas flow meter, the controller 3 is electrically connected to the methanol water raw material pump, the gas flow meter, the ceramic heating plate 12 and the thermometer 10, and the controller 3 controls the working status of the methanol water raw material pump and the ceramic heating plate 12 based on the feedback information of the gas flow meter and the thermometer 10.

[0033] Based on the feedback temperature information, the controller 3 controls the feeding time and feeding amount of the methanol water raw material pump, so that the heat absorption and heating in the reactor 5 are balanced, and the ceramic heating plate 12 is adjusted to stabilize the temperature in the reactor 5; based on the feedback flow information and the required gas output, the controller 3 controls the feeding time and feeding amount of the methanol water raw material pump, and adjusts the ceramic heating plate 12 to maintain the required gas output; thus, intelligent control of the high-efficiency methanol reforming hydrogen production device is achieved. Optionally, the controller 3 uses a PLC circuit board, etc.

[0034] The energy consumption of the methanol reforming reaction is regulated by the controller 3 to adjust the temperature of the device and the injection amount of methanol water according to the reaction conditions in the reactor 5. Since the optimal temperature for the methanol water reforming reaction efficiency is 250°C-270°C, the controller 3 needs to make adjustments according to the following conditions.

[0035] At the set gas output:

[0036] 1. When the gas output exceeds the setting, the controller 3 will reduce the injection amount of methanol water and turn off all ceramic heating plates 12. The temperature in the reactor 5 will gradually decrease, the reaction speed will slow down, and the gas output will be reduced to the set level.

[0037] 2. When the gas output is less than the set value, the controller 3 will increase the injection amount of methanol water. As the injection amount of methanol water increases, the temperature in the reactor 5 will drop sharply due to the increase in the amount of methanol water. Therefore, the controller 3 needs to increase the temperature of the ceramic heating plate 12 to accelerate the methanol water reforming reaction and increase the gas output to the set level.

[0038] 3. When the reactor 5 starts to operate, the ceramic heating plate 12 needs to be heated at full speed so that the reactor 5 reaches the ideal temperature of the methanol reforming reaction in a short time. If the amount of methanol water injection is low, the reactor 5 may overheat; if the methanol water injection is excessive, the catalyst in the reactor 5 will be covered with methanol water molecules that have not been reformed, slowing down the heating speed and consuming more energy. Therefore, the controller 3 needs to control the number and amount of methanol injection according to the real-time heating rate. When the temperature rises to the optimal temperature for the methanol reforming reaction (250℃-270℃), the controller 3 needs to control the ceramic heating plate 12 in the most energy-saving state, so that the output and temperature control of the methanol reforming reaction are balanced, and the effect of high-efficiency methanol reforming hydrogen production is achieved.

[0039] Although the present invention has been described in detail above by general description and specific embodiments, it is obvious to those skilled in the art that some modifications or improvements can be made to the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all belong to the scope of protection claimed by the present invention.

Claims

1. A high-efficiency methanol reforming hydrogen production device, characterized in that: The invention comprises a shell, a reactor, a heat exchanger, a liquid supply pipe and an exhaust pipe, wherein the shell comprises an outer shell and an inner shell arranged in the outer shell, a vacuum interlayer is arranged between the inner shell and the outer shell, the reactor is arranged in the inner shell, the heat exchanger is arranged at the front end of the shell, the heat exchanger is filled with a heat exchange medium, one end of the liquid supply pipe is connected to the liquid inlet of the reactor, the other end of the liquid supply pipe passes through the heat exchanger and is exposed, one end of the exhaust pipe is connected to the gas outlet of the reactor, the other end of the exhaust pipe passes through the heat exchanger and is exposed; The reactor comprises an inner core, an outer core, a separation tube and a ceramic heating plate, wherein the separation tube is arranged in the front-to-back direction, the separation tube separates the inner core and the outer core at the circumferential side and the rear of the inner core is connected with the outer core, the separation tube is made of corrosion-resistant metal, and the ceramic heating plate is arranged at the circumferential side of the separation tube; The reactor further includes a thermometer disposed at a front portion within the inner core; The high-efficiency methanol reforming hydrogen production device also includes a controller, the liquid inlet of the liquid supply pipe is connected to the methanol water raw material pump, the gas outlet of the exhaust pipe is connected to a gas flow meter, the controller is electrically connected to the methanol water raw material pump, the gas flow meter, the ceramic heating plate and the thermometer, the controller controls the working state of the methanol water raw material pump and the ceramic heating plate based on the feedback information of the gas flow meter and the thermometer, when the gas output is more than the setting, the controller will reduce the injection amount of methanol water and turn off all the ceramic heating plates; when the gas output is less than the setting, the controller will increase the injection amount of methanol water and increase the temperature of the ceramic heating plate; the controller controls the number and amount of methanol injection according to the real-time heating rate, and when the temperature rises to 250°C-270°C, the controller controls the ceramic heating plate to an energy-saving state; The portion of the liquid supply pipe located in the heat exchanger is distributed in a spiral shape, and the portion of the exhaust pipe located in the heat exchanger is distributed in a spiral shape.

2. The high-efficiency methanol reforming hydrogen production device according to claim 1, characterized in that: The ceramic heating plate is strip-shaped and arranged along the front-to-back direction; a plurality of the ceramic heating plates are provided, and the plurality of the ceramic heating plates are evenly distributed around the circumference of the separation cylinder.

3. The high-efficiency methanol reforming hydrogen production device according to claim 1, characterized in that: A first type of catalyst having high catalytic activity for methanol at low temperatures is placed at the front of the inner core, a second type of catalyst having high catalytic activity for methanol at high temperatures is placed at the rear of the inner core and the outer core, and a third type of catalyst having high activity for carbon monoxide is placed at the front of the outer core.

4. The high-efficiency methanol reforming hydrogen production device according to claim 1, characterized in that: The reactor further includes a nozzle, which is disposed at the front end of the inner core and is connected to the liquid supply pipe.

5. The high-efficiency methanol reforming hydrogen production device according to claim 1, characterized in that: The heat exchange medium is heat transfer oil.

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