CN115893313A - Liquid metal reactor nuclear energy coupling copper-chlorine circulation hydrogen production system and hydrogen production method - Google Patents
Liquid metal reactor nuclear energy coupling copper-chlorine circulation hydrogen production system and hydrogen production method Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 239000001257 hydrogen Substances 0.000 title claims abstract description 160
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 160
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 68
- 229910001338 liquidmetal Inorganic materials 0.000 title claims abstract description 41
- LYVWMIHLNQLWAC-UHFFFAOYSA-N [Cl].[Cu] Chemical compound [Cl].[Cu] LYVWMIHLNQLWAC-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 230000008878 coupling Effects 0.000 title claims abstract description 22
- 238000010168 coupling process Methods 0.000 title claims abstract description 22
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 116
- 238000000197 pyrolysis Methods 0.000 claims abstract description 76
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 72
- 230000007062 hydrolysis Effects 0.000 claims abstract description 61
- 238000001035 drying Methods 0.000 claims abstract description 58
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims abstract description 49
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 49
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 9
- 238000010248 power generation Methods 0.000 claims description 39
- 239000010949 copper Substances 0.000 claims description 34
- 238000003860 storage Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 10
- 238000007135 copper chlorine cycle reaction Methods 0.000 claims description 9
- 230000005611 electricity Effects 0.000 claims description 6
- 238000006073 displacement reaction Methods 0.000 claims description 4
- 238000010795 Steam Flooding Methods 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 238000013461 design Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000012546 transfer Methods 0.000 description 7
- 239000011344 liquid material Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 239000002826 coolant Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
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- 238000005265 energy consumption Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- 238000004064 recycling Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GOIGHUHRYZUEOM-UHFFFAOYSA-N [S].[I] Chemical compound [S].[I] GOIGHUHRYZUEOM-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
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- 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
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Abstract
The application provides a nuclear energy coupling copper-chlorine circulation hydrogen production system and a hydrogen production method for a liquid metal reactor, which comprise the following steps: pyrolysis apparatus for generating Cu 2 OCl 2 The steam inlet of the pyrolysis chemical reaction is connected with the secondary side outlet of the steam generator; a drying device for adding liquid CuCl 2 Drying to solid CuCl 2 (ii) a Hydrolysis device for generating solid CuCl 2 The steam outlet of the hydrolysis reaction is connected with the secondary side inlet of the steam generator; the hydrogen generating device is used for generating a replacement reaction of Cu and HCl to generate hydrogen, and a reaction discharge hole of the hydrolysis device is connected with a reaction feed hole of the hydrogen generating device; solution electrolysis device for electrolysis under electrolysis conditionsThe decomposition reaction of CuCl occurs, and the reaction discharge hole is connected with the reaction feed inlet of the hydrogen generating device; heat exchange devices are arranged among the pyrolysis device, the hydrolysis device, the drying device and the hydrogen generation device. The method combines a nuclear energy medium-temperature hydrogen production scheme and a copper-chlorine five-step method thermochemical cycle scheme, and has high hydrogen production conversion efficiency by using the residual heat of the nuclear power station.
Description
Technical Field
The application relates to the technical field of nuclear energy utilization, in particular to a liquid metal reactor nuclear energy coupling copper-chlorine circulation hydrogen production system and a hydrogen production method.
Background
Energy is one of the most important driving forces for economic growth and human development, the proposal of a double-carbon target means that the economic development further strengthens the inherent 'clean' property, the future energy economy needs to gradually replace fossil energy and reduce the emission of greenhouse gases, a low-carbon energy structure is gradually formed, and clean energy such as wind, light, water, nuclear, hydrogen and the like comes across the opportunity development period.
Hydrogen energy is an ideal secondary energy source, is mainly characterized by rich hydrogen element resources, high heat value of hydrogen gas and no pollution, and has two properties of cleanness and energy storage, the industrial chain is mainly divided into the fields of upstream hydrogen production, midstream storage and transportation, downstream application and the like, wherein the realization of large-scale production of hydrogen by utilizing primary energy in a clean and sustainable manner becomes an important ring of the premise of hydrogen energy industry development. The hydrogen gas is generated by the following three methods: 1. fossil fuel processing, 2 electrolysis of water, 3 thermochemical cycle. Wherein the fossil fuel processing is not only limited by resource reserves, but also will emit large amounts of CO 2 Waiting for greenhouse gases; the hydrogen production efficiency by water electrolysis is generally about 80%, and the hydrogen production efficiency by high-temperature electrolysis (at 1000 ℃) is only about 50%. Because the electricity charge accounts for about 80% of the production cost of the whole hydrogen production by water electrolysis, the competitiveness is not high, the key of the hydrogen production cost by water electrolysis is the problem of energy consumption, and two ways for reducing the cost are introduced: firstly, the energy consumption in the electrolytic process is reduced, and secondly, the hydrogen is produced by adopting low-cost electric power; the conventional thermochemical cycle method cannot be used for large-scale hydrogen production because a high temperature of 3000 ℃ or more is required, and also requires development of a technology capable of separating the product hydrogen and oxygen at a high temperature to avoid explosion of the gas mixture.
Disclosure of Invention
The present application is made in view of the above-mentioned technical problems. The application provides a liquid metal reactor nuclear energy coupling copper-chlorine circulation hydrogen production system and a hydrogen production method, combines a nuclear energy medium-temperature hydrogen production scheme and a copper-chlorine four-step closed thermochemical circulation scheme, and has the advantages of full utilization of the residual heat of a nuclear power station, high hydrogen production conversion efficiency and environmental friendliness.
The application in the first aspect provides a liquid metal piles nuclear energy coupling copper chlorine circulation hydrogen manufacturing system, including steam generator and power generation facility, steam generator is used for turning into the steam with the heat conversion that liquid metal piles produced and drives power generation facility electricity generation, still includes: a pyrolysis device for generating Cu 2 OCl 2 The steam inlet of the pyrolysis chemical reaction is connected with the secondary side outlet of the steam generator; a drying device for mixing liquid CuCl 2 Drying to solid CuCl 2 (ii) a A hydrolysis device for adding solid CuCl 2 Carrying out hydrolysis reaction, wherein a steam outlet of the hydrolysis reaction is connected with a secondary side inlet of the steam generator; the reaction discharge hole of the hydrolysis device is connected with the reaction feed hole of the hydrogen generation device and used for conveying HCl generated by the reaction in the hydrolysis device into the hydrogen generation device, and the hydrogen generation deviceThe displacement reaction of Cu and HCl is carried out to generate hydrogen; the solution electrolysis device is used for carrying out decomposition reaction on CuCl generated by reaction in the pyrolysis device under the electrolysis condition to provide Cu required by the reaction for the hydrogen generation device, and the solution electrolysis device is powered by the power generation device; a first heat exchange device is arranged between the pyrolysis device and the hydrolysis device and used for exchanging heat for steam discharged by the pyrolysis device, so that the steam after heat exchange is used for keeping the temperature of the hydrolysis device; a second heat exchange device is arranged between the pyrolysis device and the hydrogen generation device and used for exchanging heat of steam discharged by the pyrolysis device, so that the steam after heat exchange is used for keeping the temperature of the hydrogen generation device; and a third heat exchange device is arranged between the pyrolysis device and the drying device and used for exchanging heat for steam exhausted by the pyrolysis device, so that the steam after heat exchange is used for keeping the temperature of the drying device.
In one possible design, further comprising: the oxygen storage device is connected with the reaction discharge hole of the pyrolysis device and is used for collecting, drying and storing oxygen obtained by reaction in the pyrolysis device; the water storage device is connected with the reaction feed inlet of the hydrolysis device and supplies water for the reaction of the hydrolysis device; and the hydrogen storage device is connected with a reaction discharge hole of the hydrogen generation device and used for collecting, drying and storing hydrogen obtained by reaction in the hydrogen generation device.
In one possible design, the low-pressure cylinder exhaust pipeline of the power generation device is connected with the inlet of the first heat exchange device and/or the second heat exchange device and/or the third heat exchange device; the steam outlet of the hydrogen generating device is connected with the inlet of the first heat exchange device and/or the second heat exchange device and/or the third heat exchange device; and a steam outlet of the drying device is connected with an inlet of the first heat exchange device and/or the second heat exchange device and/or the third heat exchange device. The low-quality heat discharged from the power generation device, the hydrogen generation device, or the drying device is returned to the heat exchanger for further use.
In one possible design, the liquid metal stack outlet temperature is between 500 ℃ and 900 DEG C
In one possible design, the secondary side outlet temperature of the steam generator is 500-650 ℃ to provide a suitable temperature for the pyrolysis reaction of the subsequent pyrolysis device. The outlet temperature of a steam pipeline of the high-temperature pyrolysis device is 400-500 ℃, the outlet temperature of the first heat exchange device is 400-450 ℃, and the proper temperature is provided for the hydrolysis reaction in the subsequent hydrolysis device. The outlet temperature of the second heat exchange device is 430-475 ℃, the proper temperature is provided for the subsequent replacement reaction in the hydrogen generation device, the outlet temperature of the third heat exchange device is 90-130 ℃, and the proper temperature is provided for the subsequent drying process in the drying device.
In one possible design, the equation for the reaction occurring in the pyrolysis unit is as follows for Cu 2 OCl 2 (s)→2CuCl(1)+1/2O 2 (g) At a temperature of between 500 and 550 ℃; the reaction equation in the hydrolysis device is as follows 2CuCl 2 (s)+H 2 O(g)→Cu 2 OCl 2 (s) +2HCl (g); the equation for the reaction in the hydrogen generator is shown below as 2 Cu(s) +2HCl → 2CuCl (aq) + H 2 (g) The reaction equation generated in the drying device is CuCl 2 (aq)→CuCl 2 (s); the equation for the reaction in the solution electrolyzer is as follows 2 CuCl(s) → 2CuCl (aq) → CuCl 2 (aq)+Cu(s)。
In one possible design, the device also comprises a solid-liquid material transport system, and solid Cu produced by the reaction in the hydrolysis device is transported by the solid-liquid material transport system 2 OCl 2 Conveying into a pyrolysis device, conveying liquid CuCl generated by reaction in the pyrolysis device into a solution electrolysis device, conveying Cu generated by reaction in the solution electrolysis device into a hydrogen generation device, and conveying CuCl generated by reaction in a drying device 2 Is conveyed into a hydrolysis device. The solid-liquid substances in the whole hydrogen production system are recycled, the use efficiency is improved, the cost is saved, and the environmental pollution is reduced.
The second aspect of the application provides a method for preparing hydrogen by using a liquid metal reactor nuclear energy coupling copper-chlorine circulation hydrogen production system, which comprises the step of converting heat discharged from an outlet of a liquid metal reactor into steam through a steam generator to drive a power generation device to generate electricity, and further comprises the following steps: steam generated by the steam generator enters a steam pipeline of the pyrolysis device and provides heat for the pyrolysis chemical reaction; the steam with the temperature of 400-500 ℃ after passing through the pyrolysis device respectively enters a first heat exchange device, a second heat exchange device and a third heat exchange device, the steam with the temperature of 400-500 ℃ is converted into the steam with the temperature of 400-450 ℃ through the first heat exchange device, the steam is directly introduced into a steam pipeline of the hydrolysis device, the steam with the temperature of 400-500 ℃ is converted into the steam with the temperature of 430-475 ℃ through the second heat exchange device, the steam enters a steam pipeline of the hydrogen generation device, and the steam returns to the steam generator again after the heat of the steam is released through the hydrolysis device; converting the steam with the temperature of 400-500 ℃ into steam with the temperature of 90-130 ℃ through a third heat exchange device, and feeding the steam into a drying device; the steam entering the power generation device provides energy for power generation of the power generation device, and the electric energy generated after passing through the power generation device is provided for the solution electrolysis device for decomposition reaction.
In one possible design, the method further comprises the following steps: the steam returns to the first heat exchange device and/or the second heat exchange device and/or the third heat exchange device after the steam releases heat through a steam pipeline of the hydrogen generation device; steam discharged from a low-pressure cylinder of the power generation device enters the first heat exchange device and/or the second heat exchange device and/or the third heat exchange device; and the steam discharged from the steam outlet of the drying device enters the first heat exchange device and/or the second heat exchange device and/or the third heat exchange device.
In one possible design, the liquid metal stack outlet temperature is 500-900 ℃.
The nuclear energy coupling copper-chlorine circulation hydrogen production system and the nuclear energy coupling copper-chlorine circulation hydrogen production method are a scheme of nuclear energy coupling medium-temperature hydrogen production, the nuclear energy and the hydrogen production are organically combined, the nuclear energy and copper-chlorine chemical circulation is coupled, the stable multi-energy utilization of the nuclear energy is fully utilized, the nuclear energy coupling copper-chlorine circulation hydrogen production system and the nuclear energy coupling copper-chlorine circulation hydrogen production method are suitable for a reactor with the outlet temperature of a nuclear energy reactor core between 450 ℃ and 600 ℃, compared with the temperature of more than 1000 ℃ required by most modes of the existing thermochemical circulation hydrogen production, the requirement threshold of the nuclear energy hydrogen production is lowered, the nuclear energy hydrogen production range and the application reactor type are expanded, and a foundation is laid for large-scale nuclear energy hydrogen production. O of the reaction product in the present application 2 And H 2 Are respectively generated in different reaction stages, thereby being convenient for separation and avoiding explosion danger caused by mixing. In addition, the application has little influence on the environment compared with the common applicationThe conversion efficiency of hydrogen production is 25% -30% of the nuclear energy-electricity-hydrogen production mode, the conversion efficiency of hydrogen production reaches nearly 50%, and the hydrogen production conversion efficiency is complementary to the power generation of the nuclear power station, so that the hydrogen production conversion efficiency is supplemented, the proportion of the distribution scheme can be adjusted according to the actual market condition, and the economy of the nuclear power station is greatly improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required to be used in the embodiments of the present application will be briefly described below, and it is obvious that the drawings described below are only specific embodiments of the present application, and those skilled in the art can obtain other embodiments according to the following drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a nuclear energy coupled copper-chlorine cycle hydrogen production system of a liquid metal stack according to an embodiment of the present disclosure.
Reference numerals:
1. liquid metal pile
2. Steam generator
3. Pyrolysis device
4. First heat exchange device
5. Second heat exchanger
6. Third heat exchanger
7. Drying device
8. Hydrolysis device
9. Hydrogen generating device
10. Oxygen storage device
11. Water storage device
12. Hydrogen storage device
13. Power generation device
14. Solution electrolysis device
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present application
The embodiments are described and used in conjunction with the description to explain the principles of the application.
Detailed Description
For better understanding of the technical solutions of the present application, the following detailed descriptions of the embodiments of the present application are provided with reference to the accompanying drawings.
It should be understood that the following examples are only some of the examples of the present application. All other embodiments obtained by a person skilled in the art without making any inventive step on the basis of the following examples are within the scope of protection of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
It should be understood that the term "and/or" as used herein is merely one type of association that describes an associated object, meaning that three relationships may exist, e.g., a and/or B may mean: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the character "/" herein generally indicates that the former and latter related objects are in an "or" relationship.
It should be noted that the terms "upper", "lower", "left", "right", and the like used in the embodiments of the present application are described in terms of the angles shown in the drawings, and should not be construed as limiting the embodiments of the present application. In addition, in this context, it will also be understood that when an element is referred to as being "on" or "under" another element, it can be directly on "or" under "the other element or be indirectly on" or "under" the other element via an intermediate element.
The applicant notices that the temperature required by most modes for producing hydrogen by thermochemical circulation is above 1000 ℃, wherein the temperature required by most researches on mixed sulfur circulation and sulfur-iodine circulation is above 900 ℃, and most reactors except high-temperature gas cooled reactors have lower core outlet temperature, so that the application of nuclear reactors in thermochemical circulation hydrogen production is limited.
Based on the above problems discovered by the applicants, the present examples are further described below by selecting an appropriate thermochemical cycle method and coupling it to nuclear energy to produce hydrogen.
The embodiment of the application provides a liquid metal nuclear energy coupling copper-chlorine circulation hydrogen production system and a method for preparing hydrogen by using the system.
The liquid metal reactor is also called as a liquid metal reactor and mainly comprises a lead-cooled fast reactor, a sodium-cooled fast reactor, a molten salt reactor and the like, and can be applied to the system as long as the requirement of the outlet temperature range can be met.
Fig. 1 is a schematic structural diagram of a nuclear energy coupled copper-chlorine cycle hydrogen production system of a liquid metal stack according to an embodiment of the present disclosure.
As shown in fig. 1, the embodiment of the present application provides a nuclear energy coupled copper-chlorine cycle hydrogen production system for a liquid metal stack, which includes a steam generator 2 and a power generation device 13, wherein the steam generator 2 is used for converting heat generated by the liquid metal stack into steam to drive the power generation device 13 to generate electricity. The nuclear power plant generates electricity by using nuclear energy, the core equipment is a nuclear reactor, in the application, the nuclear reactor is a liquid metal reactor 1, heat in the liquid metal reactor 1 is brought into a steam generator 2 by coolant (also called heat carrier), a working medium on the secondary side of the steam generator 2 is heated and evaporated to form steam, the steam enters a steam turbine to expand and work, and a rotating rotor of the steam turbine drives a rotor of a power generation device 13 to rotate, so that the power generation device 13 generates electric energy.
The nuclear energy coupling copper-chlorine circulation hydrogen production system of the liquid metal reactor in the embodiment further comprises a pyrolysis device 3, a drying device 7, a hydrolysis device 8, a hydrogen generation device 9 and a solution electrolysis device 14. Pyrolysis device 3, drying device 7, hydrolysis device 8 and hydrogen generating device 9 all have steam inlet and steam outlet, keep the temperature in pyrolysis device 3, drying device 7, hydrolysis device 8 and the hydrogen generating device 9 through the steam that lets in corresponding temperature, preferably adopt and set up the steam conduit who is used for the heat transfer in pyrolysis device 3, drying device 7, hydrolysis device 8 and hydrogen generating device 9, and the both ends of steam conduit set up steam inlet and steam outlet. Pyrolysis apparatus 3 for generating Cu 2 OCl 2 The steam inlet of the steam pipeline of the pyrolysis chemical reaction is connected with the secondary side outlet of the steam generator 2; for drying devices 7After mixing liquid CuCl 2 Drying to solid state; the hydrolysis device 8 is used for generating solid CuCl 2 Has a steam pipe for heat exchange, and a steam outlet of the steam pipe is connected with a secondary side inlet of the steam generator 2; the reaction discharge hole of the hydrolysis device 8 is connected with the reaction feed hole of the hydrogen generation device 9, and is used for conveying HCl generated by the reaction in the hydrolysis device 8 to the hydrogen generation device 9, and the hydrogen generation device 9 is used for generating the replacement reaction of Cu and HCl to generate hydrogen; the solution electrolysis device 14 is used for generating a decomposition reaction of CuCl under electrolysis conditions and providing Cu required by the reaction for the hydrogen generation device 9, and the solution electrolysis device 14 is powered by the power generation device 13.
A first heat exchange device 4 is arranged between the pyrolysis device 3 and the hydrolysis device 8 and used for exchanging heat of steam discharged from a steam outlet of the pyrolysis device 3, so that the steam after heat exchange is used for maintaining the temperature of the hydrolysis device 8, and the steam after heat exchange enters a steam pipeline of the hydrolysis device 8 through a steam inlet of the hydrolysis device 8.
A second heat exchange device 5 is arranged between the pyrolysis device 3 and the hydrogen generation device 9 and used for exchanging heat for steam discharged from a steam outlet of the pyrolysis device 3, so that the steam after heat exchange is used for keeping the temperature of the hydrogen generation device 9, and the steam after heat exchange enters a steam pipeline of the hydrogen generation device 9 through a steam inlet of the hydrogen generation device 9. A third heat exchange device 6 is arranged between the pyrolysis device 3 and the drying device 7 and used for exchanging heat for the steam discharged by the pyrolysis device 3, so that the steam after heat exchange is used for keeping the temperature of the drying device 7. The steam after heat exchange by the third heat exchange device 6 enters the steam pipeline of the drying device 7 through a steam inlet of the drying device.
In this embodiment, the liquid metal pile 1 is a lead-cooled fast pile, the temperature of the coolant at the outlet of the lead-cooled fast pile is about 600 ℃, the coolant enters the steam generator 2, the steam generator 2 is a heat exchange device of the liquid metal pile 1, and the temperature of the steam at the outlet of the secondary side of the liquid metal pile reaches about 500-650 ℃. The steam inlet of the pyrolysis device 3 is connected with the secondary side outlet of the steam generator 2, and the steam discharged from the secondary side outlet of the steam generator 2 enters the steam pipeline of the pyrolysis device 3 to maintain the temperature of the pyrolysis device 3 and promote the generation of Cu in the pyrolysis device 3 2 OCl 2 The pyrolysis apparatus 3 is charged with solid Cu in advance 2 OCl 2 As the initial reaction mass, the reaction equation is as follows: cu 2 OCl 2 (s)→2CuCl(1)+1/2O 2 (g) The conditions required for the reaction are 500-550 ℃.
The temperature of the steam discharged from the steam pipeline of the pyrolysis device 3 is about 400-500 ℃, the steam enters the first heat exchange device 4, the second heat exchange device 5 and the third heat exchange device 6, the first heat exchange device 4 converts the steam with the temperature of 400-500 ℃ into the steam with the temperature of 400-450 ℃, and then the steam is introduced into the steam pipeline of the hydrolysis device 8 and is used for maintaining the temperature of the hydrolysis device 8 and promoting the solid CuCl to be generated in the hydrolysis device 8 2 The hydrolysis reaction of (1), solid CuCl is previously charged into the hydrolysis apparatus 8 2 The CuCl which is taken as the initial reaction material and is supplemented after being dried by the drying device 7 2 The reaction equation is as follows: 2CuCl 2 (s)+H 2 O(g)→Cu 2 OCl 2 (s) +2HCl (g), the conditions required for the reaction being around 420 ℃. The steam outlet of the hydrolysis device 8 is connected with the secondary inlet of the steam generator 2, and the steam with the temperature of about 400 ℃ discharged from the steam pipeline of the hydrolysis device 8 returns to the secondary inlet of the steam generator 2 to finish the closed cycle of heat.
The second heat exchange device 5 converts the steam of 400-500 ℃ into the steam of 430-475 ℃, and then the steam is introduced into a steam pipeline of the hydrogen generating device 9 to maintain the temperature of the hydrogen generating device 9, so that the HCl from the hydrolysis device 8 and the Cu from the solution electrolysis device 14 enter the hydrogen generating device 9 to be electrolyzed and generate a displacement reaction, and the reaction equation is as follows: 2 Cu(s) +2HCl → 2CuCl (aq) + H 2 (g) The reaction conditions are about 475 ℃. The reaction discharge hole of the hydrolysis device 8 is connected with the reaction feed inlet of the hydrogen generation device 9, and the hydrolysis product HCl provides raw materials for the displacement reaction.
The third heat exchange device 6 converts the steam with the temperature of 400-500 ℃ into the steam with the temperature of 90-130 ℃, and then the steam is introduced into the drying device 7 to maintain the temperature of the drying device 7, and CuCl for the initial reaction of the drying device 7 is obtained 2 CuCl coming from the solution electrolysis device 14 after reaction 2 The aqueous solution, the reaction conditions are about 100 ℃, and the reaction equation is as follows:CuCl 2 (aq)→CuCl 2 (s)。
the solution electrolysis device 14 carries out solution electrolysis on the CuCl generated by the reaction of the pyrolysis device 3 at normal temperature and normal pressure to generate solid Cu and CuCl 2 The solution, the electrical energy required for electrolysis, comes from the power generation device 13.
In one particular embodiment, the present hydrogen production system further includes an oxygen storage device 10, a water storage device 11, and a hydrogen storage device 12. The oxygen storage device 10 is connected with a reaction discharge port of the pyrolysis device 3 and is used for collecting, drying and storing oxygen generated by pyrolysis reaction in the pyrolysis device 3; the water storage device 11 is connected with the reaction feed inlet of the hydrolysis device 8 and provides water necessary for hydrolysis reaction for the hydrolysis device 8; the hydrogen storage device 12 is connected to a reaction discharge port of the hydrogen generation device 9, and is used for collecting, drying and storing hydrogen generated in the hydrogen generation device 9.
In a specific embodiment, a low-pressure cylinder exhaust pipeline of the power generation device 13 is connected with an inlet of the first heat exchange device 4 and/or the second heat exchange device 5 and/or the third heat exchange device 6, and redundant heat in the power generation device 13 is provided for the first heat exchange device 4 and/or the second heat exchange device 5 and/or the third heat exchange device 6 to be continuously utilized; a steam outlet of the drying device 7 is connected with an inlet of the first heat exchange device 4 and/or the second heat exchange device 5 and/or the third heat exchange device 6, and redundant heat after passing through the drying device 7 is provided for the first heat exchange device 4 and/or the second heat exchange device 5 and/or the third heat exchange device 6 to be continuously utilized; the steam outlet of the hydrogen generating device 9 is connected with the inlet of the first heat exchanging device 4 and/or the second heat exchanging device 5 and/or the third heat exchanging device 6, and the surplus heat after passing through the hydrogen generating device 9 is provided for the first heat exchanging device 4 and/or the second heat exchanging device 5 and/or the third heat exchanging device 6, so that the surplus heat is recycled and reused.
In a specific embodiment, the device further comprises a solid-liquid material transport system, and solid Cu produced by the reaction in the hydrolysis device 8 is transported by the solid-liquid material transport system 2 OCl 2 Is conveyed into a pyrolysis device 3 to provide raw materials for high-temperature pyrolysis reaction. The liquid CuCl produced by the reaction in the pyrolysis unit 3 is transported into a solution electrolysis unit 14 for decompositionThe raw materials should be provided. Conveying Cu generated by reaction in the solution electrolysis device 14 into the hydrogen generation device 9, and conveying CuCl generated by reaction in the solution electrolysis device 14 2 Conveyed into a drying apparatus 7, and CuCl dried in the drying apparatus 7 is also fed 2 Is transported into the hydrolysis device 8 to provide raw materials for the hydrolysis reaction. The solid-liquid substance transfer system recovers and transfers the recyclable solid-liquid products generated in each device, realizes the recycling of substances in the hydrogen production system, reduces the production cost and avoids the pollution to the environment.
The embodiment also provides a method for preparing hydrogen by using a liquid metal reactor nuclear energy coupled copper-chlorine cyclic hydrogen production system, which comprises a step of converting heat discharged from an outlet of the liquid metal reactor into steam through a steam generator 2 to drive a power generation device 13 to generate power, wherein the liquid metal reactor 1 in the embodiment is a lead-cooled fast reactor, the temperature of coolant at the outlet of the lead-cooled fast reactor is about 600 ℃, heat exchange is performed for the first time through a loop heat exchanger, the heat of the steam generator 2 is divided into two parts, one part is used for thermochemical cyclic hydrogen production, and the other part is still used for power generation, and specifically, the method further comprises the following steps:
steam generated by the steam generator 2 enters a steam pipeline of the pyrolysis device 3 to provide heat for the pyrolysis chemical reaction, and the equation of the pyrolysis chemical reaction is as follows: cu 2 OCl 2 (s)→2CuCl(1)+1/2O 2 (g) The conditions required for the reaction are 500-550 ℃. The steam with the temperature of 400-500 ℃ after passing through the pyrolysis device 3 respectively enters the first heat exchange device 4, the second heat exchange device 5 and the third heat exchange device 6, the steam with the temperature of 400-500 ℃ is converted into the steam with the temperature of 400-450 ℃ through the first heat exchange device 4, and the steam is directly introduced into a steam pipeline of the hydrolysis device 8 and is used for keeping the temperature of the hydrolysis device 8 and promoting the solid CuCl to be generated in the hydrolysis device 8 2 The reaction equation is as follows: 2CuCl 2 (s)+H 2 O(g)→Cu 2 OCl 2 (s) +2HCl (g), the conditions required for the reaction being around 420 ℃. The steam with the temperature of 400-500 ℃ is converted into the steam with the temperature of 430-475 ℃ through the second heat exchange device 5, and the steam enters a steam pipeline of the hydrogen generating device 9 and is used for maintaining the temperature of the hydrogen generating device 9 and generating the steam in the hydrogen generating device 9The crude replacement reaction has the following reaction equation: 2 Cu(s) +2HCl → 2CuCl (aq) + H 2 (g) The electrolysis was carried out under conditions of 475 ℃ or so as to obtain a reaction product. The steam is returned to the steam generator 2 again after releasing heat through the hydrolysis device 8. The steam with the temperature of 400-500 ℃ is converted into the steam with the temperature of 90-130 ℃ through the third heat exchange device 6, the steam enters the drying device 7 and is used for maintaining the temperature of the drying device 7, and a drying reaction occurs in the drying device 7, and the reaction equation is as follows: cuCl 2 (aq)→CuCl 2 (s), the reaction conditions are about 100 ℃.
The steam entering the power generation device 13 provides power for the power generation device 13, and the electric energy generated by the power generation device 13 is provided to the solution electrolysis device 14 for decomposition reaction under electrolysis conditions, wherein the reaction equation is as follows: 2 CuCl(s) → 2CuCl (aq) → CuCl 2 (aq) + Cu(s), the products obtained by the reaction provide raw materials for the reaction of the drying device 7 and the hydrogen generating device 9, respectively. .
In a specific embodiment, the method further comprises the following steps: an oxygen storage step, wherein an oxygen storage device 10 is connected with a reaction discharge hole of the pyrolysis device 3, and oxygen obtained by reaction in the pyrolysis device 3 is collected, dried and stored; a water supply step, wherein a water storage device 11 is connected with a reaction feed inlet of the hydrolysis device 8 and supplies water for the reaction of the hydrolysis device 8; and a hydrogen storage step, in which the hydrogen storage device 12 is connected with a reaction discharge hole of the hydrogen generation device 9, and hydrogen obtained by the reaction in the hydrogen generation device 9 is collected, dried and stored. The generation of oxygen in the embodiment is separated from the generation of hydrogen in the subsequent step, so that the oxygen is convenient to collect and store respectively, and the danger of explosion caused by mixing of hydrogen and oxygen is avoided.
In a specific embodiment, the method further comprises the following steps: the steam returns to the first heat exchange device 4 and/or the second heat exchange device 5 and/or the third heat exchange device 6 after the steam releases heat through a steam pipeline of the hydrogen generation device 9; the low-quality heat released by the steam pipeline of the drying device 7 returns to the first heat exchange device 4 and/or the second heat exchange device 5 and/or the third heat exchange device 6, and the redundant heat after passing through the drying device 7 is provided for the first heat exchange device 4 and/or the second heat exchange device 5 and/or the third heat exchange device 6 to be continuously utilized; the steam discharged from the low pressure cylinder of the power generation device 13 enters the first heat exchange device 4 and/or the second heat exchange device 5 and/or the third heat exchange device 6. The redundant heat recovered in the three places is respectively supplied to the hydrolysis and replacement chemical reactions in the subsequent two steps, so that the closed internal circulation of energy is realized.
In a specific embodiment, the method further comprises a solid-liquid material transfer step, wherein solid Cu generated by the reaction in the hydrolysis device 8 is transferred by a solid-liquid material transfer system 2 OCl 2 Is conveyed into a pyrolysis device 3 to provide raw materials for high-temperature pyrolysis reaction. The liquid CuCl produced by the reaction in the pyrolysis unit 3 is transported into the solution electrolysis unit 14 to provide the raw material for the decomposition reaction. Conveying Cu generated by reaction in the solution electrolysis device 14 into the hydrogen generation device 9, and conveying CuCl generated by reaction in the solution electrolysis device 14 2 Conveying the CuCl into a drying device 7, and reacting the CuCl produced in the drying device 7 2 Is sent to the hydrolysis device 8 to provide raw materials for the hydrolysis reaction. The solid-liquid substance transfer system recovers and transfers the recyclable solid-liquid products generated in each device, realizes the recycling of substances in the hydrogen production system, reduces the production cost and avoids the pollution to the environment.
The nuclear energy and hydrogen production are organically combined, the scheme of producing hydrogen at the medium temperature by using the nuclear energy is invented, the requirement threshold of producing hydrogen by using the nuclear energy is reduced, the stable multi-energy utilization of the nuclear energy is fully utilized, a large amount of heat can be directly utilized in the closed thermochemical cycle of a copper-chlorine five-step method (pyrolysis reaction, hydrolysis reaction, drying reaction, replacement reaction and decomposition reaction), reaction products can be transported by a solid-liquid substance transport device and then recycled, the influence on the environment is extremely small, the conversion efficiency of hydrogen production also reaches nearly 50%, and the hydrogen production system is complementary to power generation of a nuclear power station, not only can be supplemented, but also can be adjusted in the proportion of a distribution scheme according to the actual market condition, and the economy of the nuclear power station is greatly improved. Nuclear hydrogen production has many advantages, for example, hydrogen can be separately developed into its own market, converted into electrical energy by a fuel cell, and then sold as electrical energy during peak hours, or sold directly as chemical fuel. Another advantage is that hydrogen can be produced as an energy storage medium during off-peak periods to achieve matching of nuclear power production and demand curves. In addition, the nuclear energy hydrogen production can effectively reduce carbon emission, improve the utilization rate and competitiveness of nuclear energy, and can be coupled with new energy sources such as wind power, photovoltaics, biomass power generation and the like for application.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. The utility model provides a liquid metal piles nuclear energy coupling copper chlorine circulation hydrogen manufacturing system, includes steam generator and power generation facility, steam generator is used for turning into the steam drive with the heat that liquid metal piles produced power generation facility electricity generation, its characterized in that still includes:
a pyrolysis device for generating Cu 2 OCl 2 The steam inlet of the pyrolysis chemical reaction is connected with the secondary side outlet of the steam generator;
a drying device for adding liquid CuCl 2 Drying to solid CuCl 2 ；
A hydrolysis apparatus for hydrolyzing the solid CuCl 2 Carrying out hydrolysis reaction, wherein a steam outlet of the hydrolysis reaction is connected with a secondary side inlet of the steam generator;
the reaction discharge port of the hydrolysis device is connected with the reaction feed port of the hydrogen generation device, and the hydrogen generation device is used for conveying HCl generated by reaction in the hydrolysis device into the hydrogen generation device, and generating displacement reaction of Cu and HCl to generate hydrogen;
the solution electrolysis device is used for carrying out decomposition reaction on CuCl generated by reaction in the pyrolysis device under the electrolysis condition to provide Cu required by the reaction for the hydrogen generation device, and the solution electrolysis device is powered by the power generation device;
a first heat exchange device is arranged between the pyrolysis device and the hydrolysis device and is used for exchanging heat for steam discharged by the pyrolysis device, so that the steam after heat exchange is used for maintaining the temperature of the hydrolysis device;
a second heat exchange device is arranged between the pyrolysis device and the hydrogen generation device and is used for exchanging heat of steam discharged by the pyrolysis device, so that the steam after heat exchange is used for maintaining the temperature of the hydrogen generation device;
and a third heat exchange device is arranged between the pyrolysis device and the drying device and used for exchanging heat of the steam discharged by the pyrolysis device, so that the steam after heat exchange is used for maintaining the temperature of the drying device.
2. The system for coupling the nuclear energy of the liquid metal reactor with the copper-chlorine cycle for hydrogen production as claimed in claim 1, further comprising:
the oxygen storage device is connected with the reaction discharge hole of the pyrolysis device;
the water storage device is connected with the reaction feed inlet of the hydrolysis device;
and the hydrogen storage device is connected with the reaction discharge hole of the hydrogen generation device.
3. The liquid metal reactor nuclear energy coupling copper-chlorine cycle hydrogen production system as claimed in claim 1, characterized in that a low-pressure cylinder exhaust pipe of the power generation device is connected with an inlet of the first heat exchange device and/or the second heat exchange device and/or the third heat exchange device; the steam outlet of the hydrogen generating device is connected with the inlet of the first heat exchange device and/or the second heat exchange device and/or the third heat exchange device; and the steam outlet of the drying device is connected with the inlet of the first heat exchange device and/or the second heat exchange device and/or the third heat exchange device.
4. The system for coupling the nuclear energy and the copper-chlorine circulation hydrogen production of the liquid metal reactor as claimed in claim 1, wherein the outlet temperature of the liquid metal reactor is 500-900 ℃.
5. The liquid metal reactor nuclear energy coupling copper-chlorine cycle hydrogen production system of claim 1, wherein the secondary side outlet temperature of the steam generator is 500-650 ℃, the outlet temperature of the steam pipe of the pyrolysis device is 400-500 ℃, the outlet temperature of the first heat exchange device is 400-450 ℃, the outlet temperature of the second heat exchange device is 430-475 ℃, and the outlet temperature of the third heat exchange device is 90-130 ℃.
6. The system for coupling copper-chlorine cycle hydrogen production in a nuclear power plant of claim 1, wherein the equation for the reaction in the pyrolysis unit is as follows Cu 2 OCl 2 (s)→2CuCl(1)+1/2O 2 (g) At a temperature of between 500 and 550 ℃; the reaction equation generated in the hydrolysis device is 2CuCl 2 (s)+H 2 O(g)→Cu 2 OCl 2 (s) +2HCl (g); the reaction equation in the hydrogen generating apparatus is as follows 2 Cu(s) +2HCl → 2CuCl (aq) + H 2 (g) The reaction formula generated in the drying device is CuCl 2 (aq)→CuCl 2 (s); the equation for the reaction in the solution electrolyzer is as follows 2 CuCl(s) → 2CuCl (aq) → CuCl 2 (aq)+Cu(s)。
7. The liquid metal reactor nuclear energy coupled copper-chlorine cycle hydrogen production system as claimed in claim 1, further comprising a solid-liquid substance transport system, wherein solid Cu produced by the reaction in the hydrolysis device is transported by the solid-liquid substance transport system 2 OCl 2 Conveying into a pyrolysis device, conveying liquid CuCl generated by reaction in the pyrolysis device into the solution electrolysis device, conveying Cu generated by reaction in the solution electrolysis device into the hydrogen generation device, and conveying CuCl generated by reaction in the solution electrolysis device 2 Conveying the CuCl into a drying device, and reacting the CuCl produced in the drying device 2 Transporting into a hydrolysis device.
8. A method for preparing hydrogen by coupling liquid metal reactor nuclear energy with a copper-chlorine circulating hydrogen production system comprises the step of converting heat discharged from an outlet of a liquid metal reactor into steam through a steam generator to drive a power generation device to generate power, and further comprises the following steps:
steam generated by the steam generator enters a steam pipeline of the pyrolysis device and provides heat for pyrolysis chemical reaction; the steam with the temperature of 400-500 ℃ after passing through the pyrolysis device respectively enters a first heat exchange device, a second heat exchange device and a third heat exchange device, the steam with the temperature of 400-500 ℃ is converted into the steam with the temperature of 400-450 ℃ through the first heat exchange device, the steam is directly introduced into a steam pipeline of the hydrolysis device, the steam with the temperature of 400-500 ℃ is converted into the steam with the temperature of 430-475 ℃ through the second heat exchange device, the steam enters a steam pipeline of the hydrogen generation device, the steam returns to the steam generator again after being released by the hydrolysis device, the steam with the temperature of 400-500 ℃ is converted into the steam with the temperature of 90-130 ℃ through the third heat exchange device, and the steam enters a drying device;
the steam entering the power generation device provides energy for power generation of the power generation device, and the electric energy generated after passing through the power generation device is provided for the solution electrolysis device for decomposition reaction.
9. The method for preparing hydrogen by using the liquid metal nuclear energy coupled copper-chlorine circulation hydrogen production system as claimed in claim 8, further comprising the steps of: the steam returns to the first heat exchange device and/or the second heat exchange device and/or the third heat exchange device after passing through a steam pipeline of the hydrogen generation device to release heat; and steam discharged from a low-pressure cylinder of the power generation device enters the first heat exchange device and/or the second heat exchange device and/or the third heat exchange device, and steam discharged from a steam outlet of the drying device enters the first heat exchange device and/or the second heat exchange device and/or the third heat exchange device.
10. The method for preparing hydrogen by using the nuclear energy coupled copper-chlorine cycle hydrogen production system of the liquid metal stack as claimed in claim 8, wherein the outlet temperature of the liquid metal stack is 500-900 ℃.
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