CN114232029B - Hydrogen production system and control method for hydrogen production system - Google Patents

Hydrogen production system and control method for hydrogen production system Download PDF

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Publication number
CN114232029B
CN114232029B CN202111564789.XA CN202111564789A CN114232029B CN 114232029 B CN114232029 B CN 114232029B CN 202111564789 A CN202111564789 A CN 202111564789A CN 114232029 B CN114232029 B CN 114232029B
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heat
heat storage
loop
storage device
hydrogen production
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CN114232029A (en
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马淑杰
张延伟
马莉
郭春
赵宇峰
梅武
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Spic Hydrogen Energy Technology Development Co Ltd
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Spic Hydrogen Energy Technology Development Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C25B15/021—Process control or regulation of heating or cooling
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/60—Constructional parts of cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/60—Constructional parts of cells
    • C25B9/67—Heating or cooling means
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Inorganic Chemistry (AREA)
  • Heat-Pump Type And Storage Water Heaters (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

The invention provides a hydrogen production system and a control method of the hydrogen production system, wherein the hydrogen production system comprises an electrolyte storage device, a heat exchanger, a preheater, an electrolytic tank, a step heat storage device and a cooling device, and the electrolyte storage device, the hot side of the heat exchanger, the cold side of the preheater and the electrolytic tank are communicated to form a reaction loop; the cascade heat storage device comprises at least two heat release sides, the output temperatures among the heat release sides are different, one heat release side is communicated with the heat release side of the preheater to form a preheating loop, and the other heat release sides are connected into the heating loop in a one-to-one correspondence manner; the cold side of the heat exchanger is communicated with the heat storage side of the heat storage device to form a heat storage loop. The hydrogen production system provided by the invention effectively stores a large amount of ineffective waste heat emitted in the reaction process, realizes the recycling of low-quality heat energy, preheats electrolyte by utilizing the recycled heat, changes cold start into hot start, shortens the start time, improves the hydrogen production speed and efficiency, saves energy and reduces consumption, and reduces the operation cost.

Description

Hydrogen production system and control method for hydrogen production system
Technical Field
The application relates to the technical field of hydrogen production by water electrolysis, in particular to a hydrogen production system and a control method of the hydrogen production system.
Background
At present, common modes for producing hydrogen by water electrolysis include alkaline water electrolysis hydrogen production, proton exchange membrane water electrolysis hydrogen production and solid oxide water electrolysis hydrogen production. The alkaline water electrolysis hydrogen production technology is relatively simple, the cost is low, but the problems of low hydrogen production efficiency, low hydrogen purity and the like exist, and the electrolyte is an alkaline substance, so that the overall potential safety hazard exists. The solid oxide water electrolysis hydrogen production needs higher temperature to carry out electrolysis, and has higher energy consumption and larger heat energy loss. The proton exchange membrane water electrolysis hydrogen production technology becomes the most commonly used technical route for producing hydrogen because of the advantages of high current density, high hydrogen yield, high efficiency, system safety and the like.
However, in practical engineering application, the proton exchange membrane water electrolysis hydrogen production system has the following technical problems: firstly, cold water directly enters an electrolytic tank during cold start of a system, and electrolyte is heated by direct current, so that the reaction rate is low, the catalytic activity and the hydrogen production efficiency are low, the start time is long, and the constant temperature state of the electrolytic tank is difficult to maintain; secondly, electrolysis generates a large amount of waste heat needing to be evacuated, and the waste heat cannot be effectively recycled, so that on one hand, if the waste heat is not evacuated in time, serious problems such as membrane electrode overheating, catalyst falling-off, electrode performance attenuation and the like are generated, and on the other hand, the current heat evacuation is often realized through a cooling tower or a water chilling unit device, waste heat recovery is not performed, and the requirements of energy conservation and consumption reduction are not met.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. For this reason, the embodiment of the invention provides a hydrogen production system, and the embodiment of the invention also provides a control method of the hydrogen production system.
The hydrogen production system provided by the embodiment of the invention comprises: the electrolyte output by the electrolyte storage device releases heat at the heat exchanger to cool or absorbs heat at the preheater to heat before being input into the electrolytic tank; the heat release side of the heat storage device is communicated with the hot side of the preheater to form a preheating loop, and the heat storage device releases heat to heat electrolyte on the cold side of the preheater through the preheating loop; the cold side of the heat exchanger is communicated with the heat storage side of the heat storage device to form a heat storage loop, and heat released by the hot side of the heat exchanger is stored in the heat storage device through the heat storage loop.
The hydrogen production system provided by the invention preheats the electrolyte, changes cold start into hot start, shortens the start time, improves the hydrogen production speed and efficiency, saves energy, reduces consumption and operation cost, effectively stores a large amount of ineffective waste heat emitted by the hydrogen production system, and realizes recycling of low-quality heat energy.
In some embodiments, the hydrogen production system further comprises a cooling device coupled to the thermal storage circuit, the cooling device configured to release excess heat from the thermal storage circuit.
In some embodiments, the hydrogen production system further comprises at least one heating loop, the heat storage device is a step heat storage device, the step heat storage device comprises at least two heat release sides, the output temperatures between the heat release sides are different, one heat release side is connected to the preheating loop, and the other heat release sides are connected to the heating loops in a one-to-one correspondence.
In some embodiments, the step heat storage device comprises at least two heat storage areas and hot water pipes, the heat storage areas are respectively filled with phase change materials with different phase change temperatures, the hot water pipes penetrate through each heat storage area, the high-temperature medium in the hot water pipes releases heat to enable the phase change materials to store heat in a phase change mode, and the heat release sides of the step heat storage device are in one-to-one correspondence with the heat storage areas.
In some embodiments, the phase change temperature of the phase change material in the upstream thermal storage region is higher than the phase change temperature of the phase change material in the downstream thermal storage region.
In some embodiments, the phase change temperature of the phase change material in the heat storage zone corresponding to the heat release side of the preheating circuit is between 50 ℃ and 60 ℃.
In some embodiments, the heating circuit is used for exchanging heat with a domestic water system to heat domestic water, and the phase change temperature of the phase change material in the heat accumulation area corresponding to the heat release side connected into the heating circuit is between 30 ℃ and 50 ℃.
In some embodiments, the preheater is located at the downstream of the heat exchanger, the preheater comprises an electrolyte tube and a preheating coil, the electrolyte tube is connected into the reaction loop, the preheating coil is connected into the preheating loop, the electrolyte tube is a coiled tube, the preheating coil comprises a plurality of straight tube sections and a plurality of communicating tubes, the straight tube sections are sleeved with a part of the electrolyte tube, the straight tube sections are parallel to each other, and the communicating tubes are communicated with two adjacent straight tube sections.
In some embodiments, the hydrogen production system comprises a controller and a plurality of temperature detectors, wherein the controller is used for controlling the opening and closing of the preheating loop, the heating loop and the heat storage loop according to temperature detection signals of the temperature detectors.
In another aspect, the method for controlling a hydrogen production system provided by an embodiment of the present invention includes:
judging whether the heat storage device stores heat or not, if not, judging whether the electrolyte temperature T1 at the inlet of the electrolytic tank is smaller than a set threshold value, if so, closing the preheating loop and closing the heat storage device, if not, closing the preheating loop and opening the heat storage loop,
if the heat storage device is judged to have heat storage capacity, judging whether the electrolyte temperature T1 at the inlet of the electrolytic tank is smaller than a set threshold value, if so, opening the preheating loop and closing the heat storage loop, and if not, closing the preheating loop and opening the heat storage loop.
In some embodiments, the control method further comprises: if the heat storage device is judged to have heat storage capacity, whether the user side needs hot water supply or not is also judged, if yes, the heating loop is started, and if not, the heating loop is closed.
In some embodiments, the control method further comprises closing the preheating circuit and the heating circuit and opening the heat storage circuit if T1 is greater than or equal to a set threshold and hot water supply is not required on the user side.
Drawings
FIG. 1 is a schematic diagram of a hydrogen production system in a heating stage in accordance with an embodiment of the present invention.
FIG. 2 is a schematic diagram of a hydrogen production system in a regenerative phase in an embodiment of the invention.
Fig. 3 is a schematic diagram of a preheater according to an embodiment of the present invention.
Fig. 4 is a schematic structural view of a step heat storage device according to an embodiment of the present invention.
FIG. 5 is a flow chart of a method of controlling a hydrogen production system in accordance with an embodiment of the present invention.
Reference numerals:
1. an electrolyte storage device; 2. a heat exchanger; 3. a preheater; 31. an electrolyte tube; 32. preheating a coil; 321. a straight pipe section; 322. a communicating pipe; 4. an electrolytic cell; 5. a step heat storage device; 50. a rib; 51. a first heat accumulation zone; 511. a first filling port; 512. a first discharge port; 52. a second heat accumulation zone; 521. a second filling port; 522. a second discharge port; 53. a hot water pipe; 54. a housing; 55. an inner case; 56. a thermally insulating separator plate; 571. a first circulation zone; 572. a second circulation zone; 581. a first water outlet; 582. a first water inlet; 591. a second water outlet; 592. a second water inlet; 6. a cooling tower; 7. a circulating water pump; 8. a cooling water pump; 91. a first regulating valve; 92. a second regulating valve; 101. a first thermal resistor; 102. a second thermal resistor; 103. a third thermal resistor; 11. a controller; 12. a frequency converter; 13. and (5) an ultrapure water machine.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
The hydrogen production system and the control method of the hydrogen production system provided by the embodiment of the invention are described below with reference to fig. 1 to 5. As shown in fig. 1 and 2, the hydrogen production system provided by the embodiment of the invention comprises an electrolyte storage device 1, a heat exchanger 2, a preheater 3, an electrolytic tank 4 and a heat storage device.
The electrolyte storage device 1, the hot side of the heat exchanger 2, the cold side of the preheater 3 and the electrolytic tank 4 are communicated to form a reaction loop. The electrolyte output from the electrolyte storage device 1 releases heat at the heat exchanger 2 to cool down or absorbs heat at the preheater 3 to warm up before being input into the electrolytic tank 4. The heat-releasing side of the heat storage device is communicated with the hot side of the preheater 3 to form a preheating loop, and the heat storage device releases heat to heat the electrolyte on the cold side of the preheater 3 through the preheating loop. The cold side of the heat exchanger 2 is communicated with the heat storage side of the heat storage device to form a heat storage loop, and heat released from the hot side of the heat exchanger 2 is stored in the heat storage device through the heat storage loop.
The electrolyte storage device 1 is used for storing electrolyte, and the electrolyte storage device 1 is used for conveying the electrolyte to the electrolytic tank 4 through a reaction loop and recovering high-temperature electrolyte output after the reaction of the electrolytic tank 4. The heat exchanger 2 is used for heat exchange between the high-temperature electrolyte output by the electrolytic tank 4 and a medium in the heat storage loop when the hydrogen production system is in normal operation, the hot side of the heat exchanger 2, namely, the heat source of the side releasing heat is the high-temperature electrolyte in the reaction loop, the cold side of the heat exchanger 2, namely, the side absorbing heat is a heat exchange medium in the heat storage loop, the hot side exchanges heat to the cold side, and the heat in the high-temperature water is indirectly stored in the heat storage device through the heat exchanger 2.
The preheater 3 is used for preheating electrolyte in the reaction loop by a medium in the preheating loop in a cold start stage of the hydrogen production system, heat on the hot side of the preheater 3 is derived from heat stored in the heat storage device, the hot side exchanges heat to the cold side, the cold side of the preheater 3 is low-temperature electrolyte in the start stage, and the heat stored in the heat storage device is exchanged to the electrolyte through the preheater 3. The electrolytic tank 4 is used for water electrolysis and hydrogen preparation, and the hydrogen generated in the electrolytic tank 4 is connected to a post-treatment device for collection treatment. The heat storage device (step heat storage device 5 in this embodiment) is used for recovering the waste heat of the high-temperature water stored in the hydrogen production system through the heat storage circuit, and also for supplying the stored waste heat to the preheater 3 through the preheating device.
In the starting stage of the hydrogen production system, the temperature of electrolyte output by the electrolyte storage device 1 is lower, a preheating loop is started, heat is absorbed in the preheater 3 before the electrolyte is input into the electrolytic tank 4 for reaction, so that the temperature is increased, the preheated electrolyte enters the electrolytic tank 4 for reaction, the cold start is changed into the hot start, the starting time is shortened, the hydrogen production speed and efficiency are improved, and the purposes of energy saving and consumption reduction are achieved.
In the normal operation stage of the hydrogen production system, the preheating loop is closed, the heat storage loop is opened, the electrolyzed high-temperature electrolyte is input into the electrolyte storage device 1 from the electrolytic tank 4 along the reaction loop, and after being output from the electrolyte storage device 1, the heat is released through the heat exchanger 2, namely, the heat is exchanged to the cold side of the heat exchanger 2, the heat is stored in the heat storage device through the heat storage loop, and meanwhile, the temperature of the electrolyte is properly reduced to realize cooling.
That is, the heat storage device has a heat supply stage in which heat stored in the heat storage device is exchanged to the electrolyte through the preheating circuit to warm up and preheat the electrolyte, and a heat storage stage in which heat in the high-temperature electrolyte is stored in the heat storage device through the heat storage circuit.
The hydrogen production system provided by the invention preheats the electrolyte, changes cold start into hot start, shortens the start time, improves the hydrogen production speed and efficiency, saves energy, reduces consumption and operation cost, effectively stores a large amount of ineffective waste heat emitted by the hydrogen production system, and realizes recycling of low-quality heat energy.
A specific embodiment provided by the present invention is described below by taking fig. 1 to 5 as an example.
The hydrogen production device of the embodiment comprises an electrolyte storage device 1, a heat exchanger 2, a preheater 3, an electrolytic tank 4, a step heat storage device 5, a cooling tower 6, an ultrapure water machine 13 and a circulating water pump 7. The electrolyte is ultrapure water, and the electrolyte storage device 1 is an ultrapure water storage tank. Alternatively, the heat exchanger 2 is a plate heat exchanger.
The ultrapure water machine 13 is used for ion removal and purification of municipal water supply, and supplies ultrapure water to the electrolyte storage device 1 through a pipe. A circulating water pump 7 is provided in the reaction circuit for supplying power to the ultrapure water in the electrolyte storage device 1 and supplying the ultrapure water to the heat exchanger 2.
A cooling tower 6 is located in the thermal storage circuit for releasing excess heat in the thermal storage circuit. That is, in the normal operation stage of the hydrogen production system, the heat storage loop is opened, the heat storage of the step heat storage device 5 reaches the upper limit, the high-temperature electrolyzed water in the reaction loop needs to be cooled, and the cooling tower 6 plays a role in timely evacuating waste heat, so that the hydrogen production system is protected, and the service life is prolonged. In other embodiments, other cooling devices that act as cooling may be substituted for the cooling tower.
The inventor finds that the hydrogen production system in the related art cannot effectively match the heat consumption requirements of the factory and surrounding buildings. The industrial park where the hydrogen production system is located has the heat requirements of staff bathing and living hot water, and the surrounding areas and the like have the living hot water and heating requirements, so that the heat recovery technology such as heat storage and the like is necessary to realize the heat supply of the factory or surrounding buildings, waste is changed into valuable, and huge economic benefit is generated. And the temperature requirements of the different heat utilization ends are different, for example, the optimal temperature for preheating the electrolyte is 50-60 ℃, and the optimal temperature for domestic water (for example, bath) is 35-40 ℃. The heat storage device in the prior art generally has a single-temperature water outlet, and cannot meet the temperature requirements of different heat utilization ends.
As shown in fig. 1 and 2, the hydrogen production system in this embodiment employs a step heat storage device 5 as a heat storage device, and further includes a heating circuit. The cascade heat storage device 5 comprises two heat release sides, the output temperatures of the heat release sides are different, one heat release side is connected into the preheating loop, and the other heat release side is connected into the heating loop. The cascade heat storage device 5 can thus supply the stored waste heat to the preheater 3 via a preheating circuit, and also to other areas requiring heat via a heating circuit. In this embodiment, the heating circuit is used to heat the domestic water system to provide bath and domestic hot water for the factory and surrounding buildings.
The principle of the cascade heat storage device 5 is that the heat storage type heat exchanger and the phase change materials packaged in the heat storage type heat storage device are utilized to provide 'temperature opposite and cascade utilization' energy for different heat utilization ends by utilizing different phase change temperatures of the phase change materials. As shown in fig. 4, the step heat storage device 5 includes a first heat storage area 51 and a second heat storage area 52, and further includes a hot water pipe 53. The first heat accumulation area 51 is filled with a first phase change material, and the second heat accumulation area 52 is filled with a second phase change material. The hot water pipe 53 penetrates through the first heat storage area 51 and the second heat storage area 52, the high-temperature medium in the hot water pipe 53 is used as the heat storage side of the cascade heat storage device 5 to release heat so as to enable the phase-change material to store heat in a phase-change mode, the mediums on the two heat release sides of the cascade heat storage device 5 respectively correspond to the first heat storage area 51 and the second heat storage area 52 and absorb heat therefrom, and then the absorbed heat is respectively input into the preheating loop and the heating loop. Those skilled in the art will recognize that the output temperature on the exothermic side is equal to the phase change temperature of the phase change material, and that the output temperature between the two exothermic sides is different because the phase change temperatures of the phase change materials in the two thermal storage regions are different. The phase change material is selected according to the temperature requirements of different heat utilization terminals, so that energy of 'temperature opposite ports and gradient utilization' can be provided for the different heat utilization terminals.
As shown in fig. 4, the step heat storage device 5 has a cylindrical structure, and includes an outer shell 54 and an inner shell 55, wherein the inner shell 55 is located inside the outer shell 54, the hot water pipe 53 axially penetrates the step heat storage device 5, the inner shell 55 is sleeved with the hot water pipe 53, the inner shell 55 is coaxial with the hot water pipe 53 and defines a heat storage area with the hot water pipe 53, and a circulation area for circulating heat exchange media on a heat release side is defined between the outer shell 54 and the inner shell 55. The heat insulating partition plate 56 is located in the middle of the cascade heat storage device 5 to divide the heat storage area into the first heat storage area 51 and the second heat storage area 52 and to divide the flow area into the first flow area 571 and the second flow area 572. The first pass region 571 is connected to the preheating circuit and the second pass region 572 is connected to the heating circuit. The housing 54 is provided with a first filling port 511 for filling the first heat storage area 51 with the first phase change material, a first discharge port 512 for discharging the first phase change material from the first heat storage area 51, a second filling port 521 for filling the second heat storage area 52 with the second phase change material, and a second discharge port 522 for discharging the second phase change material from the second heat storage area 52. The housing 54 is further provided with a first water outlet 581 and a first water inlet 582 in communication with the first flow region 571, and a second water outlet 591 and a second water inlet 592 in communication with the second flow region 572.
Further, the cascade thermal storage device 5 further comprises a plurality of fins 50 provided in the flow-through area for assisting in heat conduction. The step heat storage device adopts an integrated structure, the phase change material packaging area is simple, and the connection of preheating and domestic hot water can be completed through a plurality of interfaces.
The inlet of the hot water pipe 53 is adjacent to the first heat accumulation area 51. The first heat accumulation zone 51 is also said to be located upstream of the second heat accumulation zone 52. The phase change material of the first heat storage area 51 may have a higher temperature than the phase change material of the second heat storage area 52. That is, in embodiments of the present application, the phase change temperature of the phase change material in the upstream heat storage region is higher than the phase change temperature of the phase change material in the downstream heat storage region.
This is because the preheater 3 has a higher temperature requirement than the domestic water system, so the first heat storage zone 51 corresponding to the preheating circuit preferentially abuts against the water inlet side of the hot water pipe 53, and heat storage is realized by the first phase change material having a higher phase change temperature. For the living hot water side with lower hot water temperature requirement, the heat storage is realized through the second phase change material with lower phase change temperature.
Optionally, the phase change temperature of the phase change material (first phase change material) in the heat storage area (first heat storage area 51) corresponding to the heat release side of the preheating loop is between 50 ℃ and 60 ℃, and the phase change temperature of the phase change material (second phase change material) in the heat storage area (second heat storage area 52) corresponding to the heat release side of the heating loop is between 30 ℃ and 50 ℃. Further alternatively, the phase transition temperature of the second phase change material is between 35 ℃ and 40 ℃.
Optionally, the first phase change material is paraffin C24, the phase change temperature is 51.5 ℃, the second phase change material can be paraffin C20, and the phase change temperature is 36.7 ℃.
The first phase change material and the second phase change material selected by the invention have specificity and are mainly characterized in that: firstly, the selection of the phase change material depends on the backwater temperature of the heat exchanger 2, the optimal electrolysis temperature of the electrolysis bath 4 and the required temperature of domestic hot water; secondly, the packaging areas of the two phase change materials are adjacent, the thermophysical property and the heat absorption and release rates are relatively close, and the influence of the two phase change materials is avoided; thirdly, the system aims at low-temperature waste heat phase change recovery, so that the phase change material is low in cost. The phase change material is not limited to the above-mentioned C24 and C20, and it is within the scope of the present invention for the phase change material to achieve the same effect.
It should be noted that, in other embodiments, if there are more than three heat utilization ends with different temperature requirements, the heating circuit may be provided with a plurality of heat utilization ends, the step heat storage device 5 is provided with at least three heat release sides, one heat release side is connected to the preheating circuit, and the other heat release sides are connected to the heating circuit in a one-to-one correspondence. A plurality of heat accumulating areas corresponding to the heat releasing sides one by one are also arranged in the step heat accumulating device 5, the heat accumulating areas are respectively filled with phase change materials with different phase change temperatures, and a hot water pipe 53 penetrates through each heat accumulating area.
As shown in fig. 1-3, the preheater 3 is located downstream of the heat exchanger 2, and the preheater 3 comprises an electrolyte tube 31 and a preheating coil 32, the electrolyte tube 31 being connected to the reaction circuit, and the preheating coil 32 being connected to the preheating circuit. The electrolyte tube 31 is a coiled tube, the preheating coil 32 comprises a plurality of straight tube sections 321 and a plurality of communicating tubes 322, the straight tube sections 321 are sleeved with a part of the electrolyte tube 31, the straight tube sections 321 are parallel to each other, and the communicating tubes 322 are communicated with two adjacent straight tube sections 321. In the start-up phase of the hydrogen production system, hot water enters the preheating coil 32 to exchange heat with the low-temperature electrolyte in the electrolyte pipe 31, and the electrolyte entering the electrolytic tank 4 is preheated by releasing heat, so that the electrolyte in the cold start-up phase is heated to the optimal temperature required by electrolysis. As described above, the temperature of the hot water in the pre-heat coil 32 is related to the phase transition temperature of the first phase change material, with 50-60℃ being the desired temperature for hot start-up of the hydrogen plant. The hydrogen production system is started at the temperature, so that the starting time of the hydrogen production system can be effectively shortened, the hydrogen production speed and efficiency are improved, and the energy consumption is reduced. The sleeve type preheater shown in fig. 3 fully utilizes the vertical space, reduces the horizontal occupied area and has high integration degree.
The hydrogen production system provided by the embodiment comprises a controller 11 and a plurality of temperature detectors, wherein the controller 11 is used for controlling the opening and closing of the preheating loop, the heating loop and the heat storage loop according to temperature detection signals of the temperature detectors.
Specifically, as shown in fig. 1 and 2, the hydrogen production system includes a cooling water pump 8, a first regulating valve 91, a second regulating valve 92, a first thermal resistor 101, a second thermal resistor 102, a third thermal resistor 103, and a frequency converter 12. The cooling water pump 8 is positioned in the heat storage waterway and connected between the heat exchanger 2 and the cooling tower 6 for power transmission and distribution of the heat storage loop. The frequency converter 12 is used for controlling the rotation speed and flow of the cooling water pump 8, realizing variable flow and operation energy saving, and the controller 11 controls the flow of the cooling water pump 8 by controlling the frequency converter 12.
The first regulating valve 91 is located in the preheating circuit and the second regulating valve 92 is located in the heating circuit. The controller 11 controls the start and stop of the first regulating valve 91 to start and stop the preheating circuit, and controls the start and stop of the second regulating valve 92 to start and stop the heating circuit. The controller 11 controls the start and stop of the first regulating valve 91 and the second regulating valve 92, and simultaneously controls the cascade heat storage device 5 to switch between heat storage and heat supply working conditions.
The first thermal resistor 101 is used to monitor the temperature of the first water outlet 581 of the cascade heat storage device 5, i.e. to monitor the temperature of the water supply of the cascade heat storage device 5 into the preheater 3. The second thermal resistor 102 is used for monitoring the temperature at the second water outlet 591 of the cascade heat storage device 5, i.e. monitoring the water supply temperature of the cascade heat storage device 5 for supplying heat to the domestic water system. The third thermal resistor 103 is used to monitor the temperature at the outlet of the electrolyte of the preheater 3, i.e. the temperature of the electrolyte entering the electrolytic cell 4.
The controller 11 controls each regulating valve and the cooling water pump according to the temperature detection signal to control the opening and closing of the preheating loop, the heating loop and the heat storage loop as follows:
(1) Heat supply stage of the cascade heat storage device 5:
as shown in fig. 1, the heating stage of the cascade heat storage device 5 specifically includes a preheating stage of the preheater 3 and a heating stage of the domestic hot water system.
A. When the hydrogen production system is started, as the temperature of the electrolyte is lower, the temperature collected by the third thermal resistor 103 is lower than a set value, the controller 11 judges that the water inlet temperature of the electrolytic tank 4 is too low according to the temperature detection signal collected by the third thermal resistor 103, the cooling water pump 8 and the frequency converter 12 are closed, the first regulating valve 91 and the step heat storage device 5 are opened, the preheating loop is opened, the step heat storage device 5 enters a heat supply stage, a large amount of latent heat is released by the first phase change material in the first heat storage region 51, and isothermal heat release is carried out on the preheater 3 through the preheating loop. The temperature of the electrolyte at the cold side of the preheater 3 rises after being heated, so that the temperature of the electrolyte entering the electrolytic tank 4 is raised and kept constant, and the preheating process of the electrolyte is completed;
B. when a heat user such as bath and domestic hot water in a factory or water points of buildings around the factory generates heat demand, the controller 11 opens the second regulating valve 92 and the cascade heat storage device 5, the heating circuit is opened, the cascade heat storage device 5 enters a heat supply stage, the second phase change material in the second heat storage region 52 releases a large amount of latent heat, and the domestic hot water at the user side is heated through the heating circuit to finish the supply of the domestic hot water.
(2) Heat storage stage of the cascade heat storage device 5:
the heat storage stage of the cascade heat storage device 5 is a heat storage stage of the cascade heat storage device 5 for heat storage and regeneration. The temperature that first thermal resistor 101 gathered is less than its setting value and the temperature that second thermal resistor 102 gathered is less than its setting value, and controller 11 is according to judging that the heat accumulation of step heat accumulation device 5 is spent, and specific flow is as follows:
as shown in fig. 2, the electrolyzed high-temperature hot water returns to the electrolyte storage device 1 from the electrolytic tank 4 during normal operation of the hydrogen production system, and starts to exchange heat with the heat storage loop through the heat exchanger 2 under the action of the circulating water pump 7.
The controller 11 controls the first regulating valve 91 and the second regulating valve 92 to be closed, and opens the cooling water pump 8 and the cascade heat storage device 5, so that the heat absorbed by the heat storage circuit from the heat exchanger 2 is stored in the cascade heat storage device 5, and the waste heat of electrolysis is recovered and stored.
The embodiment of the invention also provides a control method of the hydrogen production system, which comprises the following steps:
judging whether the heat storage device stores heat or not, if the heat storage device stores no heat, judging whether the electrolyte temperature T1 at the inlet of the electrolytic tank is smaller than a set threshold value, if so, closing the preheating loop and closing the heat storage device, and if not, closing the preheating loop and opening the heat storage loop;
if the heat storage device is judged to have heat storage capacity, judging whether the electrolyte temperature T1 at the inlet of the electrolytic tank is smaller than a set threshold value, if so, opening the preheating loop and closing the heat storage loop, and if not, closing the preheating loop and opening the heat storage loop; if the heat storage device is judged to have heat storage capacity, whether the user side needs hot water supply or not is also judged, if yes, the heating loop is started, and if not, the heating loop is closed;
and if T1 is greater than or equal to a set threshold value and hot water supply is not needed on the user side, closing the preheating loop and the heating loop and opening the heat storage loop.
Specifically, as shown in the flowchart of fig. 5, the control method includes:
the temperature of the discharged water of the cascade heat storage device 5 is monitored through the first thermal resistor 101 and the second thermal resistor 102, so that whether the cascade heat storage device 5 has heat storage capacity is judged, if the cascade heat storage device 5 does not have heat storage capacity, whether the detected temperature of the third thermal resistor 103 (namely, the electrolyte temperature T1 at the inlet of the electrolytic tank) is smaller than a set threshold value is judged, if yes, the controller 11 controls the first regulating valve 91 and the second regulating valve 92 to be closed, the cooling water pump 8 and the cascade heat storage device 5 are closed, namely, a preheating loop and a heating loop are closed, and the heat storage loop is closed, and because the electrolyte temperature T1 at the inlet of the electrolytic tank does not exceed the preset temperature, the heat storage and cooling flow is not easy to open, and direct current is needed to slowly heat the electrolyte in the electrolytic tank; if not, that is, if the detected temperature of the third thermal resistor 103 is greater than or equal to the set threshold, the electrolyte temperature at the inlet of the electrolytic cell is indicated to meet the reaction condition, at this time, the heat storage can be started, the controller 11 controls the first regulating valve 91 and the second regulating valve 92 to be closed, the cooling water pump 8 and the step heat storage device 5 are opened, that is, the heat storage loop is opened, and the preheating loop and the heating loop are closed;
if it is determined that the step heat storage device 5 has heat storage capacity, it is determined whether the detected temperature of the third thermal resistor 103 (i.e., the electrolyte temperature T1 at the inlet of the electrolytic cell) is less than the set threshold, if so, the controller 11 turns off the cooling water pump 8 and the inverter 12, turns on the first regulating valve 91 and the step heat storage device 5, turns on the preheating circuit, and the step heat storage device 5 enters the heating stage. When the hydrogen production system enters a normal operation stage, the detected temperature of the third thermal resistor 103 is larger than a set threshold value, the controller 11 controls the first regulating valve 91 to be closed, the cooling water pump 8 and the frequency converter 12 to be opened, the preheating loop is closed, and the heat storage loop is opened;
if it is determined that the step heat storage device 5 has heat storage capacity, it is also determined whether hot water supply is required on the user side, if so, the controller 11 controls to open the second regulating valve 92 and the step heat storage device 5, the heating circuit is opened and the step heat storage device 5 enters the heating stage, and if not, the controller 11 controls to close the second regulating valve 92, and the heating circuit is closed.
Further, the control method further includes:
after the preheating loop or the heating loop is started, whether the step heat storage device 5 stores heat is further required to be continuously judged, if the step heat storage device 5 does not store heat, whether the detection temperature of the third thermal resistor 103 (namely, the electrolyte temperature T1 at the inlet of the electrolytic tank) is smaller than a set threshold value is judged, if yes, the controller 11 controls the first regulating valve 91 and the second regulating valve 92 to be closed, and the cooling water pump 8 and the step heat storage device 5 are closed, namely, the preheating loop and the heating loop are closed, and the heat storage loop is closed, because the electrolyte temperature T1 at the inlet of the electrolytic tank does not exceed the preset temperature, the heat storage and cooling flow is not required to be started, and direct current is required to slowly heat the electrolyte in the electrolytic tank; if not, that is, if the detected temperature of the third thermal resistor 103 is greater than or equal to the set threshold, the electrolyte temperature at the inlet of the electrolytic cell is indicated to meet the reaction condition, at this time, the heat storage can be started, the controller 11 controls the first regulating valve 91 and the second regulating valve 92 to be closed, the cooling water pump 8 and the step heat storage device 5 are opened, that is, the heat storage loop is opened, and the preheating loop and the heating loop are closed;
if it is determined that the step heat storage device 5 has heat storage capacity, it is determined whether the detected temperature of the third thermal resistor 103 is less than the set threshold, if it is determined that the detected temperature is less than the set threshold, the controller 11 turns off the cooling water pump 8 and the inverter 12, turns on the first regulator valve 91 and the step heat storage device 5, and determines whether the user side needs hot water supply, if it is determined that the detected temperature of the third thermal resistor 103 is greater than or equal to the set threshold and the user side does not need hot water supply, the controller 11 controls the first regulator valve 91 and the second regulator valve 92 to be turned off, and turns on the cooling water pump 8 and the step heat storage device 5, that is, turns on the heat storage circuit and turns off the preheating circuit and the heating circuit.
In summary, the hydrogen production system and the control method thereof provided by the embodiment of the invention have the following effects:
(1) The speed and the efficiency of hydrogen production by water electrolysis are improved, electricity is saved, and the cost is reduced. The step heat storage device is utilized to heat electrolyte during cold start, the cold start is changed into hot start, the starting time is shortened, the hydrogen production speed and efficiency are improved, and the purposes of energy saving and consumption reduction are achieved.
(2) The value of low-quality energy is exerted to the maximum extent. The technology of phase change heat accumulation and cascade recovery is improved, waste heat emitted by an electrolytic water system is fully recovered, and the utilization rate of low-quality heat energy is improved; meanwhile, a sleeve type preheater is used for enhancing the heat transfer effect of water-water heat exchange, so that the utilization efficiency of low-quality heat energy is improved, and the waste of high-quality energy is reduced.
(3) The heat source is safe, stable, continuous and economical. The temperature of the hot water is safe and constant due to the constant temperature of the heat storage material during phase transition; meanwhile, the latent heat is released during phase change, the recovered heat energy is huge, the heat release time is long, and the heat release is hardly influenced by the outside. The system can provide a safe, stable, continuous and economical heat source.
(4) Obvious economic benefit. The recovered waste heat has various purposes and obvious economic value. The system can be used for preheating in the cold start stage of the system, and can be used for bathing and living hot water in factories and surrounding buildings. Meanwhile, the system has no extra operation cost and has obvious economic value.
(5) The system is simple and the occupied area is small. The cascade heat storage device in the system adopts an integrated structure, the packaging area of the phase change material is simple, and the connection between the preheating and the domestic hot water can be completed through a plurality of interfaces; the sleeve type preheater fully utilizes the vertical space and reduces the horizontal occupied area. The system saves the occupied area and has high integration degree.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element being referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the present invention.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
In the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; may be mechanically connected, may be electrically connected or may be in communication with each other; either directly or indirectly, through intermediaries, or both, may be in communication with each other or in interaction with each other, unless expressly defined otherwise. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the present invention, unless expressly stated or limited otherwise, a first feature "up" or "down" a second feature may be the first and second features in direct contact, or the first and second features in indirect contact via an intervening medium. Moreover, a first feature being "above," "over" and "on" a second feature may be a first feature being directly above or obliquely above the second feature, or simply indicating that the first feature is level higher than the second feature. The first feature being "under", "below" and "beneath" the second feature may be the first feature being directly under or obliquely below the second feature, or simply indicating that the first feature is less level than the second feature.
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.

Claims (10)

1. A hydrogen production system, comprising: electrolyte storage device, heat exchanger, preheater, electrolytic tank and heat storage device,
the electrolyte storage device, the hot side of the heat exchanger, the cold side of the preheater and the electrolytic tank are communicated to form a reaction loop, and the electrolyte output by the electrolyte storage device releases heat at the heat exchanger to reduce the temperature or absorbs heat at the preheater to raise the temperature before being input into the electrolytic tank;
the heat release side of the heat storage device is communicated with the hot side of the preheater to form a preheating loop, and the heat storage device releases heat to heat electrolyte on the cold side of the preheater through the preheating loop;
the cold side of the heat exchanger is communicated with the heat storage side of the heat storage device to form a heat storage loop, and heat released by the hot side of the heat exchanger is stored in the heat storage device through the heat storage loop;
the heat storage device comprises a heat storage area and a heat storage area, wherein the heat storage area is provided with a heat storage device, the heat storage device comprises at least two heat release sides, the output temperature between the heat release sides is different, one heat release side is connected with the preheating loop, the other heat release sides are connected with the heat storage loop in a one-to-one correspondence manner, the heat storage device comprises at least two heat storage areas and a hot water pipe, the heat storage areas are respectively filled with phase change materials with different phase change temperatures, the hot water pipe penetrates through each heat storage area, and a high-temperature medium in the hot water pipe releases heat to enable the phase change materials to store heat in a phase change mode, and the heat release sides of the heat storage device in the step form one-to-one correspondence with the heat storage areas.
2. The hydrogen production system of claim 1, further comprising a cooling device coupled to the thermal storage circuit, the cooling device configured to release excess heat from the thermal storage circuit.
3. The hydrogen production system of claim 1, wherein a phase transition temperature of the phase change material in the upstream heat storage region is higher than a phase transition temperature of the phase change material in the downstream heat storage region.
4. A hydrogen production system as claimed in claim 3 wherein the phase change material in the heat storage zone corresponding to the exothermic side of the preheating circuit has a phase change temperature between 50 ℃ and 60 ℃.
5. A hydrogen production system as claimed in claim 3 wherein the heating circuit is adapted to heat domestic water and the phase change temperature of the phase change material in the heat storage zone corresponding to the heat release side of the heating circuit is between 30 ℃ and 50 ℃.
6. The hydrogen production system of claim 1, wherein the preheater is located downstream of the heat exchanger, the preheater comprises an electrolyte tube and a preheating coil, the electrolyte tube is connected into the reaction loop, the preheating coil is connected into the preheating loop, the electrolyte tube is a coiled tube, the preheating coil comprises a plurality of straight tube sections and a plurality of communicating tubes, the straight tube sections are sleeved with a part of the electrolyte tube, the plurality of straight tube sections are parallel to each other, and the communicating tubes are communicated with two adjacent straight tube sections.
7. The hydrogen production system of claim 1, comprising a controller and a plurality of temperature detectors, wherein the controller is configured to control opening and closing of the preheating circuit, the heating circuit, and the heat storage circuit according to temperature detection signals of the temperature detectors.
8. A control method of a hydrogen production system, characterized in that the hydrogen production system is a hydrogen production system according to any one of claims 1 to 7, the control method comprising:
judging whether the heat storage device stores heat or not, if not, judging whether the electrolyte temperature T1 at the inlet of the electrolytic tank is smaller than a set threshold value, if so, closing the preheating loop and closing the heat storage device, if not, closing the preheating loop and opening the heat storage loop,
if the heat storage device is judged to have heat storage capacity, judging whether the electrolyte temperature T1 at the inlet of the electrolytic tank is smaller than a set threshold value, if so, opening the preheating loop and closing the heat storage loop, and if not, closing the preheating loop and opening the heat storage loop.
9. A control method of a hydrogen production system according to claim 8, wherein the hydrogen production system is a hydrogen production system according to claim 7, the control method comprising:
if the heat storage device is judged to have heat storage capacity, whether the user side needs hot water supply or not is also judged, if yes, the heating loop is started, and if not, the heating loop is closed.
10. The control method of a hydrogen production system according to claim 9, characterized by further comprising:
and if T1 is greater than or equal to a set threshold value and hot water supply is not needed on the user side, closing the preheating loop and the heating loop and opening the heat storage loop.
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