CN116855977A - Molten salt electrolysis hydrogen production method and system combined with fast reactor - Google Patents
Molten salt electrolysis hydrogen production method and system combined with fast reactor Download PDFInfo
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- 150000003839 salts Chemical class 0.000 title claims abstract description 189
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 77
- 239000001257 hydrogen Substances 0.000 title claims abstract description 75
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 70
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 51
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002915 spent fuel radioactive waste Substances 0.000 claims abstract description 16
- 239000003345 natural gas Substances 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 4
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910002119 nickel–yttria stabilized zirconia Inorganic materials 0.000 claims description 3
- 238000004857 zone melting Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- 239000000126 substance Substances 0.000 abstract description 9
- 238000011161 development Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 description 22
- 239000011734 sodium Substances 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
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- 229910052770 Uranium Inorganic materials 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910052768 actinide Inorganic materials 0.000 description 2
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- 238000005265 energy consumption Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000005338 heat storage Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
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- 229910052708 sodium Inorganic materials 0.000 description 2
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- 229910002076 stabilized zirconia Inorganic materials 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002927 high level radioactive waste Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N oxygen(2-);yttrium(3+) Chemical class [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
-
- 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
-
- 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
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
-
- 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
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21C—NUCLEAR REACTORS
- G21C3/00—Reactor fuel elements and their assemblies; Selection of substances for use as reactor fuel elements
- G21C3/42—Selection of substances for use as reactor fuel
- G21C3/44—Fluid or fluent reactor fuel
- G21C3/54—Fused salt, oxide or hydroxide compositions
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Plasma & Fusion (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a molten salt electrolysis hydrogen production method and system combined with a fast reactor. The structure of the molten salt electrolysis hydrogen production system is as follows: the molten salt electrolytic cell is provided with a methane air inlet and a hydrogen air outlet, electric energy of the molten salt electrolytic cell comes from a fast reactor, and heat energy comes from a heat exchanger; the heat energy of the heat exchanger comes from the heat pile; methane enters a molten salt electrolytic cell for electrolysis after passing through a heat exchanger; the molten salt electrolytic cell is connected with the dry post-treatment module so as to convey molten salt in the molten salt electrolytic cell to the dry post-treatment module; the dry post-treatment module is also connected with the fast reactor to convey the spent fuel in the fast reactor to the dry post-treatment module; the dry post-treatment module is connected with the molten salt purifying module, and the molten salt purifying module is connected with the molten salt electrolytic cell. The invention combines the electric energy and the heat energy generated by nuclear energy with fossil energy, converts the energy into chemical energy which is easy to store and transport through chemical reaction in the electrolytic cell, and has great significance for the development of nuclear industry and hydrogen energy.
Description
Technical Field
The invention relates to a molten salt electrolysis hydrogen production method and system combined with a fast reactor, belonging to the field of energy technology utilization.
Background
The structure of the human energy system is changed from the former mode of taking solid fuels such as dry plants and coal as the main materials, to the mode of taking liquid fuels such as petroleum and long-chain alkane as the main materials, and the mode of energy structure taking gases such as natural gas and hydrogen as the main materials in the future. The hydrogen energy is a secondary energy source which is rich in source, green, low in carbon and wide in application, can help the large-scale consumption of renewable energy sources, can realize large-scale cross-region energy storage of a power grid, and accelerates the low carbonization in the fields of propulsion industry, construction, traffic and the like. With the rapid development of various hydrogen energy utilization technologies represented by fuel cells, the demand of human beings for hydrogen energy will be greatly increased in the future, and the world will gradually move into the hydrogen energy era.
Methane (CH) 4 ) Is the main component of natural gas. Natural gas is abundant in the global reserve, the total reserve of the natural gas which is ascertained in the world in 2005 is 179.53 megacubic meters, and continuous exploitation and utilization of coal and petroleum by human beings causes resource shortage, so the method is a current mainstream research direction for how to efficiently utilize the natural gas to promote the structural transformation of human energy. Wherein methane is converted intoIs one of the research hot spots in the global scope at present, and is used for easily transporting and storing liquid fuel or removing hydrogen from chemical products with high added value.
The hydrogen preparation methods mainly used at present are as follows: the hydrogen produced and used in industry at present mainly comes from carbon-containing fossil fuel conversion hydrogen production, namely hydrogen synthesis gas is obtained through steam reforming of methane, the reaction is harsh in industry conditions, high-temperature and high-pressure reaction conditions are needed, the efficiency is low, the energy consumption is high, and V in the obtained synthesis gas is high (H2) /V (CO) =3, is unsuitable for important industrial processes such as synthesis of formaldehyde and Fischer-Tropsch (F-T) synthesis. Compared with the traditional steam reforming reaction, the electrolytic cell for producing hydrogen by molten salt electrolysis has small volume, high efficiency and no carbon emission, can obviously reduce equipment investment and production cost, and is one of research hot spots of the current hydrogen production technology.
Nuclear energy is an important strategic and clean energy source, and has the same important value and position as hydrogen energy. In the future of the cyclic development of nuclear fuel, the fast reactor becomes the main power generation force of the nuclear power station, and the dry post-treatment flow matched with the fast reactor becomes the main spent fuel treatment means. The main mode of nuclear energy hydrogen production at the present stage is still that a nuclear power station generates electricity and uses electrolyzed water to produce hydrogen, and in the dry post-treatment flow of a fast reactor, a molten salt system is used as solvent salt of high-emission spent fuel.
The molten alkali metal carbonate has the advantages of chemical stability, thermal stability, no toxicity, nonflammability, low operating pressure, safety, super heat storage and heat transmission capacity, lower viscosity, better fluidity, heat and mass transfer function through pipeline circulation and the like, and has been widely studied and applied in energy conversion technology. In the molten salt electrolysis process, the electrolyte has ultrahigh electron transfer efficiency and O in a molten salt system 2- The presence of ions also makes the electrolytic methane carbonization-free hydrogen production practical. The molten salt electrolysis is coupled with the fast reactor nuclear power station, so that not only can the heat source of the fast reactor be utilized, but also the fast reactor can be utilizedThe generated electric energy is used for preparing hydrogen, so that the emission of radioactive waste is reduced, the energy consumption is reduced, and the pollution to the environment is reduced.
Disclosure of Invention
The invention aims to provide a molten salt electrolysis hydrogen production method and a system combined with a fast reactor, which take a large amount of heat released by a fast reactor nuclear power station as a heat source, take molten salt as a medium and electrolyze CH (CH) 4 The method is characterized in that hydrogen is prepared without carbonization, the electrolyzed molten salt is used for post-treatment of fast reactor spent fuel, and the clean molten salt is returned to an electrolytic cell for recycling after purification, namely nuclear power molten salt chemical hydrogen production, so that the heat energy and the electric energy of a fast reactor nuclear power station are fully utilized, the consumption of fossil fuel is reduced, the emission of pollutants is reduced, the recycling of the molten salt is increased, the hydrogen production efficiency is increased, and the production cost is reduced.
The invention firstly provides a molten salt electrolysis hydrogen production system combined with a fast reactor, which comprises a molten salt electrolysis cell, a heat exchanger, a dry post-treatment module and a molten salt purification module;
the molten salt electrolysis cell is provided with a methane inlet and a hydrogen outlet button, the electric energy of the molten salt electrolysis cell is from a fast reactor, and the heat energy is from the heat exchanger;
the heat energy of the heat exchanger comes from the thermal stack;
methane enters the molten salt electrolytic cell for electrolysis after passing through the heat exchanger;
the molten salt electrolytic cell is connected with the dry post-treatment module so as to convey molten salt in the molten salt electrolytic cell to the dry post-treatment module;
the dry post-treatment module is also connected with the fast reactor to convey spent fuel in the fast reactor to the dry post-treatment module;
the dry post-treatment module is connected with the molten salt purifying module, and the molten salt purifying module is connected with the molten salt electrolytic cell.
In the molten salt electrolysis hydrogen production system, the molten salt system in the molten salt electrolysis cell is Li 2 CO-Na 2 CO 3 -K 2 CO 3 -3％Li 2 O, wherein the mass ratio of the alkali metal carbonate is as follows: li (Li) 2 CO 3 ：Na 2 CO 3 ：K 2 CO 3 ＝1：1：1。
In the molten salt electrolysis hydrogen production system, the anode material in the molten salt electrolysis cell is Ni-YSZ material, namely, ni-modified yttrium oxide stabilized zirconia is used;
the cathode material is metallic nickel which is pressed into a sheet shape and is communicated with the electrode to be inserted into the molten salt electrolytic cell, and the purity of the metallic nickel is more than 99.9 percent.
During electrolysis, the reaction occurring on the anode surface: CH (CH) 4 (g)+2O 2- →CO 2 (g)+2H 2 (g)+4e -
The capture reaction takes place inside the alkali carbonate molten salt:
the surface of the cathode reacts:
in the molten salt electrolysis hydrogen production system, the heat exchanger comprises a liquid-gas heat exchanger and a liquid-liquid heat exchanger;
the liquid-gas heat exchanger can use the heat of Na to heat CH 4 Make CH 4 Heating from room temperature to a temperature range which can be communicated with the electrolytic cell.
The liquid-liquid heat exchanger can directly use the heat of Na to heat the molten salt and supply heat to the high-temperature molten salt to maintain the reaction temperature.
In the molten salt electrolysis hydrogen production system, the molten salt purification module comprises a regional melting device, a high-temperature electrolysis device and/or a high-temperature filtering device, and impurities in molten salt are separated through various physical and chemical methods.
On the basis of the molten salt electrolysis hydrogen production system, the invention further provides a molten salt electrolysis hydrogen production method combined with a fast reactor, which comprises the following steps carried out in the system:
1) Taking heat released by the fast reactor as a heat source, and heating and melting a molten salt system in the molten salt electrolytic cell;
2) And the natural gas is introduced into the molten salt electrolytic cell after passing through the heat exchanger, and the natural gas is electrolyzed by the electric energy generated by the fast reactor to obtain C and hydrogen.
In the method of the invention, heat generated by nuclear reaction inside the fast reactor is mainly cooled and carried out by sodium in a loop, and then the sodium enters a heat exchanger module for heat exchange, so as to mainly reduce the radioactive radiation range. The molten salt used in the molten salt electrolytic cell is heated to 450-500 ℃ by a heat exchanger by heat exchanged inside the fast reactor before the reaction starts, and then is sent into the molten salt electrolytic cell, and the heat is also used for keeping the temperature inside the electrolytic cell constant. To maintain the molten salt system temperature inside the cell constant, thermocouples and electric heaters will be placed inside the cell for maintaining temperature, with power coming from the fast reactor for power generation.
In the method, molten salt in the molten salt electrolytic cell is conveyed to the dry post-treatment module to recover An and Ln in spent fuel, wherein the recovered U, pu is returned to the fast reactor for continuous use, and other radioactive impurity elements are remained in a molten salt system, so that the continuous accumulation of radioactivity can reduce the electrolytic effect and affect the purity of U, pu products, and the reaction system, namely the molten salt, needs to be purified.
The alkali metal carbonic acid fused salt after long-time electrolysis in the molten salt electrolytic cell can be used in a fast reactor spent fuel dry post-treatment module, and because the flow has a large allowable range for fused salt components, the fused salt which cannot be reused in the electrolytic cell can be used, and because the electrolytic cell has no radioactivity, the fused salt is relatively pure. It should be noted that the total amount of molten salt required by the dry post-treatment module cannot be completely supplied by the molten salt in the electrolytic cell, so that the molten salt in the cell does not need to participate in the post-treatment process from U, pu, but can be added into the purification process of any element as a supplement for supplementing the molten salt system and reducing the concentration of the element in the molten salt.
In the method, molten salt in the dry post-treatment module enters the molten salt purifying module for purification after being separated, and is then conveyed into the molten salt electrolytic cell.
In the method of the invention, the temperature in the molten salt electrolytic cell is 450-500 ℃.
The working principle of the invention for realizing molten salt electrolysis hydrogen production is as follows:
in the molten salt electrolytic cell, the heat of a heat exchanger in a fast reactor is heated to 450-500 ℃, methane is blown in from the bottom of the molten salt electrolytic cell during reaction and then contacts with an anode for reaction, and the reacted hydrogen is conveyed to a downstream factory through a hydrogen pipeline at the top of the molten salt electrolytic cell; since carbon generated from the cathode adheres to the surface of the nickel plate, the nickel plate of the cathode needs to be replaced periodically. After long electrolysis the molten salt in the molten salt electrolysis cell will be transported to a dry post-treatment module adapted to the fast reactor, where the molten salt will be used for treatment and recovery of lanthanides and actinides in spent fuel. The radioactive molten salt discharged from the dry post-treatment module is sent to a molten salt purifying module, wherein the chemical precipitation method and the electrolytic method are used for purifying impurity ions and other substances in the molten salt, and the purified molten salt is returned to an electrolytic cell for recycling.
According to the invention, by utilizing the characteristic that the molten salt electrolytic cell is similar to a molten salt system used in a dry post-treatment process, the molten salt is recycled through a molten salt purification module in the dry post-treatment process, and carbonization-free hydrogen production is realized through an electrolysis mode.
The invention has the following advantages:
the invention combines the electric energy and the heat energy generated by nuclear energy with fossil energy, converts the energy into chemical energy which is easy to store and transport through chemical reaction in the electrolytic cell, and has great significance for the development of nuclear industry and hydrogen energy.
The invention realizes carbonization-free hydrogen production in the technical field of natural gas hydrogen production, and reduces the carbon dioxide emission to zero.
The invention utilizes the characteristic that the molten salt system used in the electrolytic hydrogen production and the dry post-treatment is consistent, so that the molten salt can be recycled in the process flow, the discharge of high-level waste is reduced, and the waste of lithium resources is also reduced.
In the molten salt electrolytic cell, the chemical reaction for obtaining hydrogen by electrolyzing natural gas has little influence on the whole molten salt system, the generated carbon is easy to separate on the surface of the electrode, the process flow is simple, and the development can be realized in large scale.
Drawings
FIG. 1 is a schematic diagram of a molten salt electrolysis hydrogen production system in combination with a fast reactor of the present invention.
Detailed Description
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
As shown in FIG. 1, a schematic diagram of a fast reactor combined molten salt electrolysis hydrogen production system provided by the invention comprises a molten salt electrolysis cell, a heat exchanger, a dry post-treatment module and a molten salt purification module. The molten salt electrolysis cell is provided with a methane inlet and a hydrogen outlet, electric energy of the molten salt electrolysis cell comes from a fast reactor, heat energy of the molten salt electrolysis cell comes from a heat exchanger, heat energy of the heat exchanger comes from the heat reactor, and methane enters the molten salt electrolysis cell for electrolysis after passing through the heat exchanger. The molten salt electrolytic cell is connected with the dry post-treatment module so as to convey molten salt in the molten salt electrolytic cell to the dry post-treatment module; the dry post-treatment module is also connected with the fast reactor to convey the spent fuel in the fast reactor to the dry post-treatment module; the dry post-treatment module is connected with the molten salt purifying module, and the molten salt purifying module is connected with the molten salt electrolytic cell.
In the molten salt electrolysis hydrogen production system, a molten salt system in the molten salt electrolysis cell is Li 2 CO-Na 2 CO 3 -K 2 CO 3 -3％Li 2 O, wherein the mass ratio of the alkali metal carbonate is as follows: li (Li) 2 CO 3 ：Na 2 CO 3 ：K 2 CO 3 =1: 1:1. the anode material in the molten salt electrolytic cell is Ni-YSZ material, namely Ni is used for modificationYttria stabilized zirconia; the cathode material is metallic nickel which is pressed into a sheet shape and is communicated with the electrode to be inserted into the molten salt electrolytic cell, and the purity of the metallic nickel is more than 99.9 percent.
During electrolysis, the reaction occurring on the anode surface: CH (CH) 4 (g)+2O 2- →CO 2 (g)+2H 2 (g)+4e -
The capture reaction takes place inside the alkali carbonate molten salt:
the surface of the cathode reacts:
in the fused salt electrolysis hydrogen production system, the heat exchanger is an integrated module, in the heat exchanger, the heat exchanged by Na in a fast reactor loop is also used for preheating cold natural gas, the natural gas is heated to above room temperature to improve the safety of the reaction, a liquid-gas heat exchanger and a liquid-liquid heat exchanger are arranged in the heat exchanger, and the liquid-gas heat exchanger can use the heat of Na for heating CH 4 Make CH 4 The temperature range from room temperature to the temperature range which can be led into the electrolytic cell is heated, and the liquid-liquid heat exchanger can directly use the heat of Na to heat the molten salt and supply heat to the high-temperature molten salt to maintain the reaction temperature.
In the molten salt electrolysis hydrogen production system, the molten salt purification module comprises a regional melting device, a high-temperature electrolysis device and/or a high-temperature filtering device, and various physical and chemical methods are used for separating impurities in molten salt.
The process of producing hydrogen by electrolysis by using the molten salt electrolysis hydrogen production system of the invention is as follows:
(1) heat in the fast reactor is exchanged into a molten salt electrolytic cell by utilizing a heat exchanger, so that the temperature of molten salt in the molten salt electrolytic cell reaches 450-500 ℃, and CH is introduced from the bottom of the molten salt electrolytic cell 4 Gas, CH 4 Electrolytic reaction in molten salt to generate C and H 2 . (2) After long-time electrolysis, molten salt is discharged from a molten salt electrolytic cell and enters a dry post-treatment module, and An in fast reactor spent fuel are recoveredLn. (3) The molten salt is separated and enters a molten salt purifying module after passing through a post-treatment module, and is sent into a molten salt electrolytic cell for recycling after being purified by chemical reaction.
Example 1 normal operation of the fast reactor and electrolytic cell
As shown in FIG. 1, the molten salt electrolysis hydrogen production system is utilized for carrying out electrolysis hydrogen production.
In the operation process of the fast reactor, the energy mainly comprises two parts, namely heat and electricity, wherein the electric energy is emitted by a steam turbine in a second loop in the reactor, one part of the electric energy is directly supplied to an electrolytic cell, and the heat energy is radioactive and needs to be transferred to a non-heat-storage material by a heat exchanger to be transferred to the molten salt electrolytic cell to be used as a heat source. In the electrolytic cell module, the continuous electric energy and heat energy of the fast reactor are supplied, wherein natural gas is simply preheated and then is blown into molten salt from the bottom of the electrolytic cell, CH 4 Is electrolyzed into C and H through electrolytic reaction 2 Wherein C is deposited on the surface of the cathode plate, H 2 Generated at the anode and collected through a hydrogen pipe.
When the inside of the fast reactor is not stopped and the electrolytic cell does not need to be replaced with molten salt, the process is repeated to realize continuous electrolysis hydrogen production.
Example 2 operating conditions during fast reactor parking
As shown in FIG. 1, the molten salt electrolysis hydrogen production system is utilized for carrying out electrolysis hydrogen production.
In the fast reactor stopping process, fuel in the reactor is discharged to enter a spent fuel post-treatment flow, meanwhile, the molten salt electrolytic cell stops the electrolysis process, gas transmission is stopped, new molten salt is replaced, molten salt after long-time reaction directly enters the spent fuel post-treatment flow in a molten state, in the flow, old molten salt is taken as solvent salt to dissolve the discharged spent fuel in the reactor, and lanthanoid and actinoid elements in the spent fuel are recovered through electrolysis, chemical precipitation and other reactions in the post-treatment flow. In the molten salt purifying module, the molten salt is purified by a chemical method, the impurities in the molten salt are removed, the molten salt is reduced to be in a purer state, the molten salt can be directly returned to an electrolytic cell for reuse if the fast reactor is started, the molten salt can be kept stand until the molten salt is cooled if the fast reactor is not started, and the molten salt is melted when the fast reactor is started to start the electrolytic hydrogen production process.
Example 3: operating conditions during fast reactor driving
As shown in FIG. 1, the molten salt electrolysis hydrogen production system is utilized for carrying out electrolysis hydrogen production.
After fast reactor is started and generates heat and electricity, the molten salt in the electrolytic cell is heated by a heat exchanger to be completely melted, and then CH is introduced 4 Gas, CH by heat exchanger 4 Heating to above room temperature, then blowing into the electrolytic cell, and electrifying again to start the electrolytic hydrogen production flow after the gas is continuously blown into the electrolytic cell.
Claims (9)
1. A molten salt electrolysis hydrogen production system combined with a fast reactor comprises a molten salt electrolysis cell, a heat exchanger, a dry post-treatment module and a molten salt purification module;
the molten salt electrolysis cell is provided with a methane air inlet and a hydrogen air outlet, the electric energy of the molten salt electrolysis cell is from a fast reactor, and the heat energy is from the heat exchanger;
the heat energy of the heat exchanger comes from the thermal stack;
methane enters the molten salt electrolytic cell for electrolysis after passing through the heat exchanger;
the molten salt electrolytic cell is connected with the dry post-treatment module so as to convey molten salt in the molten salt electrolytic cell to the dry post-treatment module;
the dry post-treatment module is also connected with the fast reactor to convey spent fuel in the fast reactor to the dry post-treatment module;
the dry post-treatment module is connected with the molten salt purifying module, and the molten salt purifying module is connected with the molten salt electrolytic cell.
2. The molten salt electrolysis hydrogen production system of claim 1, wherein: the molten salt system in the molten salt electrolytic cell is Li 2 CO-Na 2 CO 3 -K 2 CO 3 -3％Li 2 O, wherein the mass ratio of the alkali metal carbonate is：Li 2 CO 3 ：Na 2 CO 3 ：K 2 CO 3 ＝1：1：1。
3. The molten salt electrolysis hydrogen production system according to claim 1 or 2, characterized in that: the anode material in the molten salt electrolytic cell is Ni-YSZ material, and the cathode material is metallic nickel.
4. A molten salt electrolysis hydrogen production system according to any one of claims 1 to 3, wherein: the heat exchanger comprises a liquid-gas heat exchanger and a liquid-liquid heat exchanger.
5. The molten salt electrolysis hydrogen production system according to any one of claims 1-4, wherein: the molten salt purification module comprises a zone melting device, a high-temperature electrolysis device and/or a high-temperature filtering device.
6. A molten salt electrolysis hydrogen production process in combination with a fast reactor comprising the steps performed in the system of any one of claims 1-5 of:
1) Taking heat released by the fast reactor as a heat source, and heating and melting a molten salt system in the molten salt electrolytic cell;
2) And the natural gas is introduced into the molten salt electrolytic cell after passing through the heat exchanger, and the natural gas is electrolyzed by the electric energy generated by the fast reactor to obtain C and hydrogen.
7. The molten salt electrolysis hydrogen production method according to claim 6, wherein: molten salt in the molten salt electrolytic cell is conveyed to the dry post-treatment module to recover An and Ln in spent fuel.
8. The molten salt electrolysis hydrogen production method according to claim 7, wherein: and separating molten salt in the dry post-treatment module, purifying the separated molten salt in the molten salt purifying module, and then conveying the separated molten salt to the molten salt electrolytic cell.
9. The molten salt electrolysis hydrogen production method according to any one of claims 6 to 8, wherein: the temperature in the molten salt electrolytic cell is 450-500 ℃.
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