CN114232029A - 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
CN114232029A
CN114232029A CN202111564789.XA CN202111564789A CN114232029A CN 114232029 A CN114232029 A CN 114232029A CN 202111564789 A CN202111564789 A CN 202111564789A CN 114232029 A CN114232029 A CN 114232029A
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heat
heat storage
loop
storage device
hydrogen production
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CN114232029B (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)
  • Inorganic Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Heat-Pump Type And Storage Water Heaters (AREA)

Abstract

The invention provides a hydrogen production system and a control method thereof, 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, wherein 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 of the heat release sides are different, one of the heat release sides is communicated with the heat side of the preheater to form a preheating loop, and the other heat release sides are connected to 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 the electrolyte by using the recycled heat, changes 'cold start' into 'hot start', shortens the start time, improves the hydrogen production speed and efficiency, saves energy, 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, the commonly used water electrolysis hydrogen production modes include alkaline water electrolysis hydrogen production, proton exchange membrane water electrolysis hydrogen production and solid oxide water electrolysis hydrogen production. The hydrogen production technology by alkaline electrolysis of water is relatively simple and has low cost, but has the problems of low hydrogen production efficiency, low hydrogen purity and the like, and the electrolyte is an alkaline substance, so that the whole process has potential safety hazards. The hydrogen production by water electrolysis of solid oxide requires higher temperature for electrolysis, and has higher energy consumption and larger heat energy loss. The proton exchange membrane hydrogen production technology by water electrolysis is the most common technical route for producing hydrogen due to 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 the electrolytic cell when the system is in cold start, and the electrolyte is heated by direct current, so that the reaction rate is low, the catalytic activity and hydrogen production efficiency are low, the starting time is long, and the constant temperature state of the electrolytic cell is difficult to maintain; secondly, a large amount of waste heat which needs to be evacuated is generated by electrolysis, 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 overheating of a membrane electrode, falling of a catalyst, attenuation of electrode performance and the like are generated, and on the other hand, the existing heat evacuation is usually realized by a cooling tower or a water chilling unit device, the waste heat recovery is not performed, and the requirements of energy conservation and consumption reduction are not met.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, 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 device comprises an electrolyte storage device, a heat exchanger, a preheater, an electrolytic cell and a heat storage device, wherein the electrolyte storage device, the hot side of the heat exchanger, the cold side of the preheater and the electrolytic cell are communicated to form a reaction loop, and the electrolyte output by the electrolyte storage device releases heat in the heat exchanger to reduce the temperature or absorbs heat in the preheater to increase the temperature before being input into the electrolytic cell; 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 the 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, reduces the operation cost, effectively stores a large amount of ineffective waste heat emitted by the hydrogen production system, and realizes the recycling of low-quality heat energy.
In some embodiments, the hydrogen production system further comprises a cooling device connected to the heat storage loop, the cooling device being configured to release excess heat from the heat storage loop.
In some embodiments, the hydrogen production system further comprises at least one heating loop, the heat storage device is a stepped heat storage device, the stepped heat storage device comprises at least two heat release sides, the output temperatures of the heat release sides are different, one of the heat release sides is connected into the preheating loop, and the other heat release sides are connected into the heating loop in a one-to-one correspondence manner.
In some embodiments, the step heat storage device comprises at least two heat storage areas and hot water pipes, wherein 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, a high-temperature medium in the hot water pipes releases heat to enable the phase change materials to store heat in a phase change manner, and the heat release sides of the step heat storage device correspond to the heat storage areas one to one.
In some embodiments, 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.
In some embodiments, the phase change temperature of the phase change material in the heat storage region coupled to the heat release side of the preheat loop is between 50 ℃ and 60 ℃.
In some embodiments, the heating loop 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 storage area corresponding to the heat release side connected into the heating loop is between 30 ℃ and 50 ℃.
In some embodiments, the preheater is located downstream of the heat exchanger, the preheater includes an electrolyte tube and a preheating coil, the electrolyte tube is connected to the reaction loop, the preheating coil is connected to the preheating loop, the electrolyte tube is a coiled tube, the preheating coil includes a plurality of straight tube sections and a plurality of communicating tubes, a part of the electrolyte tube is sleeved on the straight tube sections, the straight tube sections are parallel to each other, and the communicating tubes communicate 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 preheating loop, the heating loop and the heat accumulation loop to be opened and closed according to temperature detection signals of the temperature detectors.
In another aspect, the present invention provides a method for controlling a hydrogen production system, comprising:
judging whether the heat storage device has heat storage quantity, if not, judging whether the temperature T1 of the electrolyte at the inlet of the electrolytic bath is less 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,
and if the heat storage device is judged to have the heat storage capacity, judging whether the temperature T1 of the electrolyte at the inlet of the electrolytic cell is less than a set threshold value, if so, starting 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: and if the heat storage device has the heat storage capacity, judging whether the user side needs hot water supply, if so, starting the heating loop, and if not, closing the heating loop.
In some embodiments, the control method further comprises closing the pre-heat loop and the heating loop and opening the thermal storage loop if T1 is greater than or equal to a set threshold and the hot water supply is not required on the user side.
Drawings
FIG. 1 is a schematic diagram of a hydrogen production system in a heat supply stage according to an embodiment of the present invention.
FIG. 2 is a schematic diagram of the hydrogen production system in the heat accumulation stage in the embodiment of the present invention.
FIG. 3 is a schematic diagram of a preheater according to an embodiment of the present invention.
Fig. 4 is a schematic structural diagram of a stepped heat storage device in an embodiment of the invention.
FIG. 5 is a schematic flow diagram of a method for controlling a hydrogen production system in 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 pipe; 321. a straight pipe section; 322. a communicating pipe; 4. an electrolytic cell; 5. a step heat storage device; 50. ribs; 51. a first heat storage zone; 511. a first fill port; 512. a first discharge port; 52. a second heat storage zone; 521. a second fill port; 522. a second discharge port; 53. a hot water pipe; 54. a housing; 55. an inner shell; 56. a heat insulating partition plate; 571. a first flow-through zone; 572. a second flow-through 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 water circulating 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 resistance; 11. a controller; 12. a frequency converter; 13. an ultra-pure 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 with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
A hydrogen production system and a method for controlling the hydrogen production system according to an embodiment of the present invention will be described below with reference to fig. 1 to 5. As shown in fig. 1 and 2, a hydrogen production system according to an embodiment of the present invention includes an electrolyte storage device 1, a heat exchanger 2, a preheater 3, an electrolytic bath 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 cell 4 are communicated to form a reaction loop. The electrolyte output from the electrolyte storage device 1 releases heat in the heat exchanger 2 to reduce the temperature or absorbs heat in the preheater 3 to increase the temperature before being input into the electrolytic cell 4. The heat-releasing side of the heat storage device is communicated with the heat 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 by the hot side of the heat exchanger 2 is stored in the heat storage device through the heat storage loop.
Electrolyte storage device 1 is used for storing electrolyte, and electrolyte storage device 1 carries electrolyte to electrolysis trough 4 through the reaction return circuit to and retrieve the high temperature electrolyte of output after the electrolysis trough 4 reacts. The heat exchanger 2 is used for heat exchange between high-temperature electrolyte output by the electrolytic cell 4 and a medium in the heat storage loop when the hydrogen production system normally operates, the heat source of the hot side of the heat exchanger 2, namely 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 the 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.
Preheater 3 is arranged in hydrogen manufacturing system cold start phase, and the medium in the preheating loop preheats the electrolyte in the reaction loop, and the heat of the hot side of preheater 3 derives from the heat of storing in the heat storage device, and the hot side gives the cold side with heat exchange, and the cold side of preheater 3 is the low temperature electrolyte of start phase, and through preheater 3, the heat exchange of storing in the heat storage device gives electrolyte. The electrolytic cell 4 is used for electrolysis of water and preparation of hydrogen, and the hydrogen generated in the electrolytic cell 4 is connected to a post-treatment device for collection and treatment. The heat storage device (the stepped heat storage device 5 in the present embodiment) is used to recover the waste heat of the high-temperature water of the storage hydrogen production system through the heat storage circuit and also to supply the stored waste heat to the preheater 3 through the preheating device.
At the starting stage of the hydrogen production system, the temperature of the electrolyte output by the electrolyte storage device 1 is lower, the preheating loop is started, before the electrolyte is input into the electrolytic bath 4 for reaction, heat is absorbed in the preheater 3 so as to increase the temperature, the preheated electrolyte enters the electrolytic bath 4 for reaction, the cold start is changed into the hot start, the starting time is shortened, the hydrogen production speed and efficiency are increased, and the purposes of energy conservation 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 bath 4 along the reaction loop, heat is released through the heat exchanger 2 after being output from the electrolyte storage device 1, 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 it up for preheating, 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, reduces the operation cost, effectively stores a large amount of ineffective waste heat emitted by the hydrogen production system, and realizes the recycling of low-quality heat energy.
An embodiment of the present invention will be 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 bath 4, a step heat storage device 5, a cooling tower 6, an ultra-pure 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. Optionally, the heat exchanger 2 is a plate heat exchanger.
The ultrapure water machine 13 is used for ion removal and purification of municipal water, and supplies ultrapure water to the electrolyte storage device 1 through a pipe. The circulating water pump 7 is positioned in the reaction loop and used for providing distribution power for the ultrapure water in the electrolyte storage device 1 and delivering the ultrapure water to the heat exchanger 2.
A cooling tower 6 is located in the heat storage circuit for releasing excess heat from the heat storage circuit. That is to say, 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 the waste heat, so that the hydrogen production system is protected, and the service life is prolonged. In other embodiments, other cooling devices that provide cooling may be substituted for the cooling tower.
The inventors have discovered that hydrogen production systems of the related art do not effectively match the heat requirements of the plant and surrounding structures. The industrial park where the hydrogen production system is located has heat requirements of staff for bathing and domestic hot water, and peripheral districts and the like also have domestic hot water and heating requirements, so that heat recovery technologies such as heat storage and the like are necessary to realize heat supply of the plant area or peripheral buildings, waste is changed into valuable, and great economic benefit is generated. Also, the temperature requirements vary from hot end to hot end, for example the optimum temperature for electrolyte pre-heating is 50-60 ℃ and the optimum temperature for domestic water (e.g. bathing) is 35-40 ℃. The heat storage device in the traditional technology is generally single-temperature water, and cannot meet the temperature requirements of different heat using terminals.
As shown in fig. 1 and fig. 2, the hydrogen production system in this embodiment uses a stepped heat storage device 5 as a heat storage device, and further includes a heating loop. The step heat storage device 5 comprises two heat release sides, the output temperature of the heat release sides is different, one of the heat release sides is connected to the preheating loop, and the other heat release side is connected to the heating loop. The stepped heat storage device 5 can thus supply the stored waste heat to the preheater 3 via the preheating circuit, but also to other areas requiring heat via the heating circuit. In this embodiment, the heating circuit is used to heat a domestic water system to provide bathing and domestic hot water for buildings in and around the plant area.
The principle of the step heat storage device 5 is that different phase-change temperatures of the phase-change materials are utilized through the heat storage type heat exchanger and the phase-change materials packaged in the heat storage type heat exchanger, and energy of 'temperature alignment and step utilization' is provided for different heat utilization tail ends. As shown in fig. 4, the step heat storage device 5 includes a first heat storage region 51 and a second heat storage region 52, and further includes a hot water pipe 53. The first heat storage region 51 is filled with a first phase change material, and the second heat storage region 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, a high-temperature medium in the hot water pipe 53 is used as a heat storage side of the step heat storage device 5 to release heat so as to enable the phase change material to store heat in a phase change manner, the media of the two heat release sides of the step heat storage device 5 respectively correspond to the first heat storage area 51 and the second heat storage area 52 and absorb heat from the first heat storage area 51 and the second heat storage area 52, and then the absorbed heat is respectively input into the preheating loop and the heating loop. As will be appreciated by those skilled in the art, the output temperature of the heat-releasing side is equal to the phase change temperature of the phase change material, and thus the output temperature between the two heat-releasing sides is different due to the different phase change temperatures of the phase change materials in the two heat storage regions. The phase-change material is selected according to the temperature requirements of different heat using terminals, so that the energy of 'temperature to mouth and gradient utilization' can be provided for the different heat using terminals.
As shown in fig. 4, the step heat storage device 5 is a cylindrical structure, and includes an outer shell 54 and an inner shell 55, the inner shell 55 is located inside the outer shell 54, the hot water pipe 53 axially penetrates through the step heat storage device 5, the hot water pipe 53 is sleeved on the inner shell 55, 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 a heat exchange medium on the 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 stepped heat storage device 5 and divides the heat storage region into the first heat storage region 51 and the second heat storage region 52, and the flow region into the first flow-through region 571 and the second flow-through region 572. The first flow-through area 571 is connected to the preheating circuit, and the second flow-through area 572 is connected to the heating circuit. The housing 54 is provided with a first charge port 511 for charging the first phase-change material into the first heat storage region 51, a first discharge port 512 for discharging the first phase-change material from the first heat storage region 51, a second charge port 521 for charging the second phase-change material into the second heat storage region 52, and a second discharge port 522 for discharging the second phase-change material from the second heat storage region 52. The housing 54 is further provided with a first water outlet 581 and a first water inlet 582 communicating with the first flow-through region 571, and a second water outlet 591 and a second water inlet 592 communicating with the second flow-through region 572.
Further, the stepped thermal storage device 5 further includes a plurality of fins 50 disposed in the circulation area for assisting in heat conduction. The step heat storage device adopts an integrated structure, the phase change material packaging area is simple to separate, and the connection between 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 storage region 51. It can also be said that the first heat storage zone 51 is located upstream of the second heat storage zone 52. The phase change material of first heat storage region 51 may have a higher temperature than the phase change material of second heat storage region 52. That is, in the embodiment of the present application, the phase change temperature of the phase change material in the heat storage region located upstream is higher than the phase change temperature of the phase change material in the heat storage region located downstream.
This is because the preheater 3 has a higher temperature demand than the domestic water system, and therefore the first heat storage region 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 domestic hot water side with low hot water temperature demand, heat storage is realized through the second phase change material with low phase change temperature.
Alternatively, the phase change temperature of the phase change material (first phase change material) in the heat storage region (first heat storage region 51) corresponding to the heat release side connected to the preheat circuit is between 50 ℃ and 60 ℃, and the phase change temperature of the phase change material (second phase change material) in the heat storage region (second heat storage region 52) corresponding to the heat release side connected to the heat circuit is between 30 ℃ and 50 ℃. Further optionally, the second phase change material has a phase change temperature between 35 ℃ and 40 ℃.
Alternatively, the first phase-change material is paraffin C24 with the phase-change temperature of 51.5 ℃, and the second phase-change material can adopt paraffin C20 with the phase-change temperature of 36.7 ℃.
The first phase change material and the second phase change material selected by the invention have particularity and are mainly embodied in the following three points: firstly, the selection of the phase-change material depends on the return water temperature of the heat exchanger 2, the optimal electrolysis temperature of the electrolytic bath 4 and the required temperature of domestic hot water; secondly, the packaging areas of the two phase-change materials are adjacent, the thermophysical properties and the heat absorption and release rates are relatively close, and the mutual influence is avoided; thirdly, the system aims at low-temperature waste heat phase change recovery, so the phase change material is low in price. The phase change material is not limited to the above-mentioned C24 and C20, and the phase change material capable of achieving the same effect is within the scope of the present invention.
It should be noted that, in other embodiments, if there are more than three heat using terminals with different temperature requirements, the heating circuit may be provided in plurality, and the step heat storage device 5 is provided with at least three heat releasing sides, where one heat releasing side is connected to the preheating circuit, and the other heat releasing sides are connected to the heating circuit in a one-to-one correspondence manner. A plurality of heat storage areas corresponding to the heat release sides one by one are also arranged in the step heat storage device 5, phase change materials with different phase change temperatures are respectively filled in the heat storage areas, and the hot water pipe 53 penetrates through each heat storage area.
As shown in fig. 1-3, the preheater 3 is located downstream of the heat exchanger 2, the preheater 3 comprising 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 includes a plurality of straight tube sections 321 and a plurality of communicating tubes 322, a part of the electrolyte tube 31 is sleeved with the straight tube sections 321, the straight tube sections 321 are parallel to each other, and the communicating tubes 322 communicate two adjacent straight tube sections 321. In the starting stage of the hydrogen production system, hot water enters the preheating coil 32 to exchange heat with the low-temperature electrolyte in the electrolyte tube 31, the heat is released to preheat the electrolyte entering the electrolytic cell 4, and the electrolyte in the cold starting stage is heated to the optimal temperature required by electrolysis. As described above, the temperature of the hot water in preheat coil 32 is related to the phase change temperature of the first phase change material, with 50-60 ℃ being the ideal 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 preheater shown in fig. 3 makes full use of the vertical space, reduces the horizontal floor space, 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 an inverter 12. And the cooling water pump 8 is positioned in the heat storage water path, is connected between the heat exchanger 2 and the cooling tower 6 and is used for power transmission and distribution of the heat storage loop. The frequency converter 12 is used for controlling the rotating speed and flow of the cooling water pump 8, so that flow changing and operation energy saving are achieved, and the controller 11 controls the frequency converter 12 to control the flow of the cooling water pump 8.
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 realize the start and stop of the preheating loop, and controls the start and stop of the second regulating valve 92 to realize the start and stop of the heating loop. The controller 11 controls the start and stop of the first regulating valve 91 and the second regulating valve 92, and simultaneously controls the switching of the step heat storage device 5 between the heat storage working condition and the heat supply working condition.
The first thermal resistor 101 is used for monitoring the temperature of the first water outlet 581 of the step heat storage device 5, i.e. monitoring the temperature of the water supplied by the step heat storage device 5 to the preheater 3. The second thermal resistor 102 is used for monitoring the temperature at the second water outlet 591 of the step heat storage device 5, i.e. the temperature of the water supplied by the step heat storage device 5 to the domestic water system. The third thermal resistance 103 is used to monitor the temperature at the electrolyte outlet of the preheater 3, i.e. the temperature of the electrolyte entering the electrolytic cell 4.
The controller 11 controls the regulating valves and the cooling water pump to control the preheating loop, the heating loop and the heat storage loop to be opened and closed according to the temperature detection signal as follows:
(1) heating phase of the step heat storage device 5:
as shown in fig. 1, the heating phase of the stepped heat storage device 5 specifically includes a preheating phase of the preheater 3 and a heating phase of the domestic hot water system.
A. When the hydrogen production system starts, because the temperature of the electrolyte is low, 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 cell 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, the first phase change material in the first heat storage area 51 releases a large amount of latent heat, and isothermal heat release is performed on the preheater 3 through the preheating loop. The temperature of the electrolyte on the cold side of the preheater 3 rises after being heated, so that the temperature of the electrolyte entering the electrolytic cell 4 is increased and constant, and the preheating process of the electrolyte is completed;
B. when a hot user needs to generate heat for bathing and domestic hot water consumption points in a plant area or water consumption points of buildings around the plant area, the controller 11 opens the second regulating valve 92 and the step heat storage device 5, the heating loop is opened, the step heat storage device 5 enters a heat supply stage, the second phase change material in the second heat storage area 52 releases a large amount of latent heat, and domestic hot water on the user side is heated through the heating loop, so that domestic hot water is supplied.
(2) Heat storage stage of the stepped heat storage device 5:
the heat storage stage of the step heat storage device 5 is actually a heat re-storage stage when the heat storage amount of the step heat storage device 5 is used up. When the temperature collected by the first thermal resistor 101 is lower than the set value and the temperature collected by the second thermal resistor 102 is lower than the set value, the controller 11 determines that the heat storage amount of the step heat storage device 5 is used up, and the specific flow is as follows:
as shown in fig. 2, high-temperature hot water after electrolysis in normal operation of the hydrogen production system returns to the electrolyte storage device 1 from the electrolytic tank 4, 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, the cooling water pump 8 and the step heat storage device 5 are opened, the heat absorbed by the heat storage loop from the heat exchanger 2 is stored in the step heat storage device 5, and the ineffective 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 has heat storage capacity, if the heat storage device does not have heat storage capacity, judging whether the temperature T1 of the electrolyte at the inlet of the electrolytic cell 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 the heat storage capacity, judging whether the temperature T1 of the electrolyte at the inlet of the electrolytic cell is smaller than a set threshold value, if so, starting 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 the heat storage capacity, whether the user side needs hot water supply is also judged, if so, the heating loop is started, and if not, the heating loop is closed;
if T1 is greater than or equal to the set threshold and hot water supply is not needed on the user side, the preheating loop and the heating loop are closed, and the heat storage loop is opened.
Specifically, as shown in the flowchart shown in fig. 5, the control method includes:
monitoring the outlet water temperature of the step heat storage device 5 through the first thermal resistor 101 and the second thermal resistor 102 to further judge whether the step heat storage device 5 has heat storage amount, if the step heat storage device 5 has no heat storage amount, judging whether the detected temperature of the third thermal resistor 103 (namely the electrolyte temperature T1 at the inlet of the electrolytic cell) is smaller than a set threshold value, if so, controlling the first regulating valve 91 and the second regulating valve 92 to be closed by the controller 11, and closing the cooling water pump 8 and the step heat storage device 5, namely closing the preheating loop and the heating loop and closing the heat storage loop, because the electrolyte temperature T1 at the inlet of the electrolytic cell does not exceed the preset temperature at the moment, the heat storage and cooling process is not suitable to be started, and direct current is required to slowly heat the electrolyte in the electrolytic cell; if not, namely if the detected temperature of the third thermal resistor 103 is greater than or equal to the set threshold, which indicates that the temperature of the electrolyte at the inlet of the electrolytic cell meets the reaction condition, heat storage can be started at this time, and 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 started, namely the heat storage loop is started and the preheating loop and the heating loop are closed;
if it is determined that the step heat storage device 5 has the heat storage amount, it is determined whether the detected temperature of the third thermal resistor 103 (i.e., the temperature T1 of the electrolyte at the inlet of the electrolytic cell) is less than a set threshold, and if so, the controller 11 turns off the cooling water pump 8 and the frequency converter 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 heat supply stage. When the hydrogen production system enters a normal operation stage, the detection temperature of the third thermal resistor 103 is greater 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 the step heat storage device 5 is judged to have the heat storage amount, and whether the user side needs hot water supply is also judged, if yes, the controller 11 controls to open the second regulating valve 92 and the step heat storage device 5, the heating loop is opened, and the step heat storage device 5 enters a heat supply stage, if not, the controller 11 controls to close the second regulating valve 92, and the heating loop is closed.
Further, the control method further comprises:
after the preheating loop or the heating loop is started, whether the heat storage amount of the step heat storage device 5 exists or not needs to be continuously judged, if the step heat storage device 5 does not have the heat storage amount, whether the detection temperature of the third thermal resistor 103 (namely the electrolyte temperature T1 at the inlet of the electrolytic cell) is smaller than a set threshold value or not 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 cell does not exceed the preset temperature at the moment, the heat storage and cooling process is not suitable to be started, and the electrolyte in the electrolytic cell needs to be slowly heated by direct current; if not, namely if the detected temperature of the third thermal resistor 103 is greater than or equal to the set threshold, which indicates that the temperature of the electrolyte at the inlet of the electrolytic cell meets the reaction condition, heat storage can be started at this time, and 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 started, namely the heat storage loop is started and the preheating loop and the heating loop are closed;
if it is determined that the stepped heat storage device 5 has the heat storage amount, it is determined whether the detected temperature of the third thermal resistor 103 is less than a set threshold value, 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 stepped heat storage device 5, and determines whether the user side requires hot water supply, if so, the controller 11 controls the second regulating valve 92 and the stepped heat storage device 5 to be turned on, and if the detected temperature of the third thermal resistor 103 is greater than or equal to the set threshold value and the user side does not require hot water supply, the controller 11 controls the first regulating valve 91 and the second regulating valve 92 to be turned off, and turns on the cooling water pump 8 and the stepped heat storage device 5, that is, turns on the heat storage loop and turns off the preheating loop and the heating loop.
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 electrolyte is heated by the step heat storage device during cold start, the cold start is changed into hot start, the start time is shortened, the hydrogen production speed and efficiency are improved, and the purposes of energy conservation and consumption reduction are achieved.
(2) The value of low-quality energy is exerted to the maximum extent. The technology of phase change heat storage and cascade recovery is improved, waste heat emitted by the electrolytic water system is fully recovered, and the utilization rate of low-quality heat energy is improved; meanwhile, the sleeve type preheater is used for enhancing the heat transfer effect of water-water heat exchange, improving the utilization efficiency of low-quality heat energy and reducing the waste of high-quality energy.
(3) The heat source is safe, stable, continuous and economical. Because the temperature is constant when the heat storage material is in phase change, the temperature of the hot water is safe and constant; meanwhile, latent heat is released during phase change, the recovered heat energy is huge, the heat release time is long, and the heat-exchange plate is hardly influenced by the outside. Therefore, the system can provide a safe, stable, continuous and economic heat source.
(4) The economic benefit is obvious. The recovered waste heat has various purposes and obvious economic value. On one hand, the system can be used for preheating in a cold start stage of the system, and on the other hand, the system can be used for bathing and domestic hot water of factories and surrounding buildings. Meanwhile, the system has no extra operation cost and very obvious economic value.
(5) The system is simple and the occupied area is small. The step heat storage device in the system adopts an integrated structure, the phase-change material packaging area is simple to separate, and the connection between preheating and domestic hot water can be completed through a plurality of interfaces; the sleeve type preheater fully utilizes the vertical space and reduces the horizontal floor area. The system saves the occupied area and has high integration degree.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be considered limiting of the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; may be mechanically coupled, may be electrically coupled or may be in communication with each other; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the present invention, unless otherwise expressly stated or limited, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through an intermediate. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer 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, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (12)

1. A hydrogen production system, comprising: an electrolyte storage device, a heat exchanger, a preheater, an electrolytic tank and a heat storage device,
the electrolyte storage device, the hot side of the heat exchanger, the cold side of the preheater and the electrolytic cell are communicated to form a reaction loop, and the electrolyte output by the electrolyte storage device releases heat in the heat exchanger to reduce the temperature or absorbs heat in the preheater to increase the temperature before being input into the electrolytic cell;
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 the 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.
2. The hydrogen production system as claimed in claim 1, further comprising a cooling device connected to the heat storage loop, the cooling device being configured to release excess heat from the heat storage loop.
3. The hydrogen production system according to claim 1, further comprising at least one heating loop, wherein the heat storage device is a stepped heat storage device, the stepped heat storage device comprises at least two heat release sides, the output temperatures of the heat release sides are different, one of the heat release sides is connected to the preheating loop, and the other heat release sides are connected to the heating loop in a one-to-one correspondence manner.
4. The hydrogen production system according to claim 3, wherein 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, a high-temperature medium in the hot water pipes releases heat to enable the phase change materials to store heat in a phase change manner, and the heat release sides of the step heat storage device correspond to the heat storage areas one by one.
5. The hydrogen production system according to claim 4, wherein 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.
6. The hydrogen production system according to claim 4 or 5, wherein the phase change temperature of the phase change material in the heat storage region connected to the heat release side of the preheating circuit is between 50 ℃ and 60 ℃.
7. The hydrogen production system according to any one of claims 4 or 5, wherein the heating loop is used for heating domestic water, and the phase change temperature of the phase change material in the heat storage region corresponding to the heat release side connected into the heating loop is between 30 ℃ and 50 ℃.
8. The hydrogen production system as claimed in claim 1, wherein the preheater is located downstream of the heat exchanger, the preheater includes an electrolyte tube and a preheating coil, the electrolyte tube is connected to the reaction loop, the preheating coil is connected to the preheating loop, the electrolyte tube is a coiled tube, the preheating coil includes a plurality of straight tube sections and a plurality of communicating tubes, the straight tube sections are sleeved on a portion of the electrolyte tube, the straight tube sections are parallel to each other, and the communicating tubes communicate two adjacent straight tube sections.
9. The hydrogen production system according to claim 3, comprising a controller and a plurality of temperature detectors, wherein the controller is used for controlling the preheating loop, the heating loop and the heat storage loop to be opened and closed according to temperature detection signals of the temperature detectors.
10. A method for controlling a hydrogen production system according to any one of claims 1 to 9, the method comprising:
judging whether the heat storage device has heat storage quantity, if not, judging whether the temperature T1 of the electrolyte at the inlet of the electrolytic bath is less 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,
and if the heat storage device is judged to have the heat storage capacity, judging whether the temperature T1 of the electrolyte at the inlet of the electrolytic cell is less than a set threshold value, if so, starting the preheating loop and closing the heat storage loop, and if not, closing the preheating loop and opening the heat storage loop.
11. The method for controlling a hydrogen production system according to claim 10, wherein the hydrogen production system is a hydrogen production system according to claim 7, and the method for controlling comprises:
and if the heat storage device has the heat storage capacity, judging whether the user side needs hot water supply, if so, starting the heating loop, and if not, closing the heating loop.
12. The method of controlling a hydrogen generation system according to claim 11, further comprising:
if T1 is greater than or equal to the set threshold and hot water supply is not needed on the user side, the preheating loop and the heating loop are closed, and the heat storage loop is opened.
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