CN118028830A - Tower type solar photo-thermal coupling solid oxide water electrolysis hydrogen production heat system - Google Patents
Tower type solar photo-thermal coupling solid oxide water electrolysis hydrogen production heat system Download PDFInfo
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- CN118028830A CN118028830A CN202410206655.8A CN202410206655A CN118028830A CN 118028830 A CN118028830 A CN 118028830A CN 202410206655 A CN202410206655 A CN 202410206655A CN 118028830 A CN118028830 A CN 118028830A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000007787 solid Substances 0.000 title claims abstract description 101
- 239000001257 hydrogen Substances 0.000 title claims abstract description 68
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 68
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 50
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 44
- 230000008878 coupling Effects 0.000 title claims abstract description 20
- 238000010168 coupling process Methods 0.000 title claims abstract description 20
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 176
- 238000005338 heat storage Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 230000001105 regulatory effect Effects 0.000 claims description 38
- 239000007789 gas Substances 0.000 claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 238000005485 electric heating Methods 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 230000008646 thermal stress Effects 0.000 claims description 3
- 238000013021 overheating Methods 0.000 claims description 2
- 238000009825 accumulation Methods 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 6
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000012267 brine Substances 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910002119 nickel–yttria stabilized zirconia Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 230000026676 system process Effects 0.000 description 1
Classifications
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention relates to a tower type solar photo-thermal coupling solid oxide water electrolysis hydrogen production and heating system, which comprises: the system comprises a fused salt heat storage type tower solar photo-thermal module, a first heat exchange module, a second heat exchange module, a solid oxide electrolyzed water hydrogen production module and a water supply module; the fused salt heat accumulation type tower solar photo-thermal module is used for heat collection and heat accumulation and comprises: heliostat field, solar heat collecting tower, high temperature molten salt tank, molten salt pump I, low temperature molten salt tank and molten salt pump II; the cathode air inlet of the solid oxide electrolytic cell is connected with the air outlet of the electric heater. Compared with the prior art, the fused salt heat storage type tower solar photo-thermal system is introduced to produce hydrogen and heat for solid oxide electrolyzed water, has a simpler structure, enhances the flexibility of the hydrogen production system and has wide application scene; the energy utilization efficiency is high, the waste of exhaust heat is reduced, and the higher hydrogen production efficiency of the system is obtained.
Description
Technical Field
The invention relates to the technical field of tower type solar heat collection and water electrolysis hydrogen production, in particular to a tower type solar photo-thermal coupling solid oxide water electrolysis hydrogen production heat system.
Background
The insufficient renewable energy source digestion capability is an important difficult problem faced by people under the current 'double carbon' target, and the hydrogen production by water electrolysis by utilizing waste wind and waste light is considered to have wide application prospect. In the existing water electrolysis hydrogen production technology, the working temperature of the solid oxide electrolysis technology is usually above 600 ℃, the hydrogen production efficiency, the electrolysis efficiency and the hydrogen production per unit area of the system are improved compared with those of alkaline electrolysis and proton exchange membrane electrolysis, and the technology is the only technology capable of reversibly operating an electric pile at present, and has the potential of large-scale application in the future.
Patent CN202110564164.7 discloses a high-temperature solid oxide electrolytic water hydrogen production system and process coupled with solar energy amino thermochemical energy storage and kalina cycle, the system comprises an amino thermochemical energy system, a kalina cycle system and a high-temperature solid oxide electrolytic water hydrogen production system, the amino thermochemical energy system and the high-temperature solid oxide electrolytic water hydrogen production system are in heat exchange connection through a sixth heat exchanger, a third heat exchanger and a seventh heat exchanger, the amino thermochemical energy system and the kalina cycle system are in heat exchange connection through a fifth heat exchanger, and the kalina cycle system is connected with the high-temperature solid oxide electrolytic water hydrogen production system to provide raw materials for the high-temperature solid oxide electrolytic water hydrogen production system. However, the technical scheme of the patent has complex structure and pipeline arrangement and low flexibility. Patent CN202311151521.2 discloses a solar energy heat and power combined hydrogen production system based on a solid oxide electrolytic cell, which belongs to the technical field of solar energy water electrolysis hydrogen production, and comprises a water storage tank, a main water transmission pump, a medium temperature solar heat collector, a starting hydrogen storage tank, a heat exchanger, an ejector, a high temperature solar heat collector, a solid oxide electrolytic cell, a high temperature steam-hydrogen separator, a water-gas separator, a condensate water circulating pump, a vacuum pump, a compressor and a hydrogen storage tank. The invention adopts the two-stage solar heat collector to generate high-temperature steam, and realizes the primary separation of the steam and the hydrogen in a high-temperature environment through the high-temperature hydrophobic hydrogen permeable membrane; the ejector is used for refluxing high-temperature electrolysis tail gas, so that the utilization rate of high-temperature steam is improved, and a reducing atmosphere is provided for the cathode of the electrolytic cell; and a vacuum pump is introduced into a normal-temperature pipeline, the backflow flow of the ejector is reliably regulated and controlled by regulating the pressure, and the fluctuation air inlet requirement of solar hydrogen production is met. However, the technical scheme of the patent has lower energy utilization efficiency and lower hydrogen production efficiency of the system.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a tower type solar photo-thermal coupling solid oxide electrolytic water hydrogen production heat system, wherein a fused salt heat storage type tower type solar photo-thermal system is introduced to produce hydrogen and heat for solid oxide electrolytic water, has a simpler structure, enhances the flexibility of the hydrogen production system and has wide application range; the energy utilization efficiency is high, the waste of exhaust heat is reduced, and the higher hydrogen production efficiency of the system is obtained.
The aim of the invention can be achieved by the following technical scheme:
For solid oxide cells, both electrical energy and high temperature thermal energy are required, so coupling with solar heat is an ideal way of coupling in terms of thermal systems. The tower type solar thermal system has the characteristics of large light concentration ratio, high temperature parameter, large system capacity and high efficiency, and is relatively matched with the solid oxide electrolytic cell in the aspects of temperature matching and the like. Because the coupled hydrogen production system needs to operate at high temperature, the structure of the thermal system is generally complex, and the outlet gas of the electrolytic cell has higher temperature, so that the outlet heat can be fully utilized, the temperature of the exhaust system gas is reduced, the waste of the exhaust heat is reduced, and the higher hydrogen production efficiency of the system is obtained.
The invention provides a tower type solar photo-thermal coupling solid oxide water electrolysis hydrogen production and heating system, which comprises: the system comprises a fused salt heat storage type tower solar photo-thermal module, a first heat exchange module, a second heat exchange module, a solid oxide electrolyzed water hydrogen production module and a water supply module;
The fused salt heat accumulation type tower solar photo-thermal module is used for heat collection and heat accumulation and comprises: heliostat field, solar energy heat collecting tower, high temperature salt melting tank, low temperature salt melting tank; the heliostat field reflects sunlight to the solar heat collection tower to collect heat and heat molten salt, a molten salt outlet of the solar heat collection tower is connected with a molten salt inlet of the high-temperature molten salt tank, and a molten salt outlet of the low-temperature molten salt tank is connected with a molten salt inlet of the solar heat collection tower;
The molten salt outlet of the high-temperature molten salt tank is connected with the molten salt inlet of the first heat exchange module, and the molten salt inlet of the low-temperature molten salt tank is connected with the molten salt outlet of the first heat exchange module;
The solid oxide water electrolysis hydrogen production module comprises: the cathode air inlet of the solid oxide electrolytic cell is connected with the air outlet of the electric heater; the cathode air outlet and the anode air outlet of the solid oxide electrolytic cell are connected with the first air inlet of the second heat exchange module; the first air outlet of the second heat exchange module is connected with the air inlet of the electric heater, and the second air outlet of the second heat exchange module is connected with the outside of the system;
The water outlet of the water supply module is respectively connected with the water inlet of the first heat exchange module and the water inlet of the second heat exchange module, and the air outlet of the first heat exchange module is connected with the second air inlet of the second heat exchange module.
Further, a molten salt pump I is arranged between the molten salt outlet of the high-temperature molten salt tank and the molten salt inlet of the first heat exchange module, and a molten salt pump II is arranged between the molten salt outlet of the low-temperature molten salt tank and the molten salt inlet of the solar heat collection tower.
Further, the first heat exchange module comprises a superheater I, an evaporator I and a preheater I which are sequentially connected, a molten salt inlet of the low-temperature molten salt tank is connected with a molten salt outlet of the preheater I, and a molten salt outlet of the high-temperature molten salt tank is connected with a molten salt inlet of the superheater I. The water is preheated to saturation temperature in the preheater I, then is sent into the evaporator I for endothermic evaporation, and is sent into the superheater I for overheating after evaporation. The high-temperature molten salt sent out by the molten salt pump I sequentially exchanges heat with cold flow through the superheater I, the evaporator I and the preheater I, and the high-temperature molten salt after heat exchange flows into the low-temperature molten salt tank.
Further, the second heat exchange module comprises a preheater II, an evaporator II, a superheater II and a superheater III which are sequentially connected, the water outlet of the water supply module is respectively connected with the water inlet of the preheater I and the water inlet of the preheater II, and the air outlet of the superheater I is connected with the second air inlet of the superheater III; the water is preheated to saturation temperature in a preheater II, then is sent into an evaporator II to absorb heat and evaporate, and is sent into a superheater II to be superheated after evaporation.
Further, the cathode of the solid oxide electrolytic cell is connected with the air outlet of the electric heater, and the superheated steam fed into the cathode generates hydrogen at the cathode and oxygen at the anode through electrochemical reaction. High-temperature hydrogen discharged from a cathode gas outlet of the solid oxide electrolytic cell and unreacted superheated steam and high-temperature oxygen discharged from an anode gas outlet sequentially pass through a superheater III, a superheater II, an evaporator II and a preheater II to exchange heat with cold flow, and finally are discharged from a system to be collected.
Further, still include tee bend confluence governing valve, tee bend confluence governing valve includes: the air inlet I is connected with the air outlet of the superheater I, the air inlet II is connected with the air outlet of the superheater II, and the air outlet of the three-way confluence regulating valve is connected with the second air inlet of the superheater III. The air inlet I is filled with superheated steam from the superheater I, the air inlet II is filled with superheated steam from the superheater II, the superheated steam is sent into the superheater III from the air outlet after being converged, and the air outlet of the superheater III is connected with the air inlet of the electric heater.
Further, still include three-way shunt regulator valve, three-way shunt regulator valve includes: the water inlet of the three-way shunt regulating valve is connected with the water supply module.
Further, the water supply module comprises a water tank and a water pump which are connected.
Further, the solid oxide electrolytic cell is connected with external direct current, and is electrolyzed by introducing direct current from the outside, and under different electric power input, the solid oxide electrolytic cell has three working modes according to the magnitude relation of inlet and outlet temperatures: inputting first electric power, and working in an endothermic mode, wherein the temperature of a cathode air inlet of the solid oxide electrolytic cell is higher than the temperatures of a cathode air outlet and an anode air outlet of the solid oxide electrolytic cell, and in the mode, the available heat of the cathode outlet gas and the anode outlet gas of the electrolytic cell is less, more electric heating cathode inlet superheated steam is needed, and the hydrogen production amount is minimum; inputting second electric power, and working in a thermal neutral mode, wherein the temperature of a cathode air inlet of the solid oxide electrolytic cell is equal to the temperatures of a cathode air outlet and an anode air outlet of the solid oxide electrolytic cell, a small amount of electric heating cathode inlet superheated steam is required in the mode, and thermal stress is not generated in the electrolytic cell to influence the service life of the electrolytic cell; and inputting third electric power, and working in an exothermic mode, wherein the temperature of a cathode air inlet of the solid oxide electrolytic cell is lower than the temperatures of a cathode air outlet and an anode air outlet of the solid oxide electrolytic cell, and in the mode, the available heat of the cathode outlet gas and the anode outlet gas of the electrolytic cell is more, and the cathode inlet superheated steam is not required to be electrically heated in a certain temperature range.
The heat storage part of the system is double-tank direct heat storage, and molten salt in the high-temperature molten salt tank and the low-temperature molten salt tank is used as a heat transfer medium for heat exchange with cold flow and is also used as a heat storage medium. And concentrating the heat in the heliostat field, sending the heat into a solar heat collection tower to heat molten salt from a low-temperature molten salt tank, and heating the molten salt and then storing the molten salt in a high-temperature molten salt tank. And during electrolysis, the high-temperature molten salt is output by a molten salt pump I and sequentially passes through a superheater I, an evaporator I and a preheater I to exchange heat with cold flow for three times, the cooled molten salt enters a low-temperature molten salt tank, and then is sent into a solar heat collection tower by a molten salt pump II to absorb heat and raise temperature to complete circulation.
The brine heat exchange process formed by the preheater I, the evaporator I and the superheater I and the heat exchange process formed by the preheater II, the evaporator II and the superheater II of the solid oxide electrolytic cell are respectively carried out in parallel, the outlet heat flow of the anode and the heat exchange process of the water are respectively carried out, the water outlet II of the three-way shunt regulating valve is closed at the initial stage of system starting, the water fed out of the water tank through the water feeding pump is all fed into the preheater I, the water tank exchanges heat with high-temperature molten salt for three times in the preheater I, the evaporator I and the superheater I to become superheated steam, and then the superheated steam is fed into the electric heater through the three-way confluence regulating valve and the superheater III in sequence to be heated to the temperature required by electrolysis, and then enters the solid oxide electrolytic cell to carry out electrolysis; along with the progress of electrolytic reaction, after the solid oxide electrolytic cell cathode and anode outlet heat flows are stably output, a three-way shunt regulating valve water outlet II is opened, the shunt of a water outlet I and a water outlet II is regulated to a proper proportion, and the high-temperature molten salt mass flow is regulated through a molten salt pump I, so that the heat exchange can be carried out with cold flow respectively by utilizing a parallel structure formed by the high-temperature molten salt heat flow and the solid oxide electrolytic cell cathode and anode outlet heat flows.
Compared with the prior art, the invention has the following advantages:
(1) The fused salt heat storage type tower solar photo-thermal system is introduced to supply heat for hydrogen production by solid oxide electrolyzed water, has a simpler structure, enhances the flexibility of the hydrogen production system and has wide application range.
(2) The energy utilization efficiency is high, the waste of exhaust heat is reduced, and the higher hydrogen production efficiency of the system is obtained. In the initial stage of system start, high-temperature fused salt heat flow and electric heating are used for providing high-temperature steam for the electrolytic cell, and after stable operation, the high-temperature fused salt heat flow and the cathode and anode outlet gas heat flows of the electrolytic cell are subjected to step-by-step heat exchange by a parallel structure at corresponding temperature levels, and the heat release quantity of each heat flow is reasonably distributed by adjusting the water tank water supply split ratio and the high-temperature fused salt flow, so that the cathode and anode outlet gas heat of the electrolytic cell is fully utilized for carrying out the internal heat exchange of the system process, and the temperature of discharged system gas can be reduced.
Drawings
FIG. 1 is a schematic diagram of a tower solar photo-thermal coupling solid oxide water electrolysis hydrogen production thermal system.
Reference numerals: 1-heliostat field, 2-solar heat collection tower, 3-high temperature molten salt tank, 4-molten salt pump I, 5-low temperature molten salt tank, 6-molten salt pump II, 7-water tank, 8-water supply pump, 9-three-way split flow regulating valve, 10-preheater I11-evaporator I, 12-superheater I, 13-preheater II, 14-evaporator II, 15-superheater II, 16-three-way confluence regulating valve, 17-superheater III, 18-electric heater and 19-solid oxide electrolytic cell.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. Features such as a part model, a material name, a connection structure, a control method, an algorithm and the like which are not explicitly described in the technical scheme are all regarded as common technical features disclosed in the prior art.
Example 1
The embodiment provides a tower type solar photo-thermal coupling solid oxide water electrolysis hydrogen production heat system, which comprises: the system comprises a fused salt heat storage type tower solar photo-thermal module, a first heat exchange module, a second heat exchange module, a solid oxide electrolyzed water hydrogen production module and a water supply module, and is particularly shown in fig. 1.
The fused salt heat accumulation type tower solar photo-thermal module is used for heat collection and heat accumulation and comprises: heliostat field 1, solar heat collection tower 2, high-temperature molten salt tank 3 and low-temperature molten salt tank 5; the heliostat field 1 reflects sunlight to the solar heat collection tower 2 to collect heat and heat molten salt, a molten salt outlet of the solar heat collection tower 2 is connected with a molten salt inlet of the high-temperature molten salt tank 3, and a molten salt outlet of the low-temperature molten salt tank 5 is connected with a molten salt inlet of the solar heat collection tower 2;
the molten salt outlet of the high-temperature molten salt tank 3 is connected with the molten salt inlet of the first heat exchange module, and the molten salt inlet of the low-temperature molten salt tank 5 is connected with the molten salt outlet of the first heat exchange module;
The solid oxide water electrolysis hydrogen production module comprises: the electric heater 18 and the solid oxide electrolytic cell 19, and a cathode air inlet of the solid oxide electrolytic cell 19 is connected with an air outlet of the electric heater 18; the cathode air outlet and the anode air outlet of the solid oxide electrolytic cell 19 are both connected with the first air inlet of the second heat exchange module; the first air outlet of the second heat exchange module is connected with the air inlet of the electric heater 18, and the second air outlet of the second heat exchange module is connected with the outside of the system;
The water outlet of the water supply module is respectively connected with the water inlet of the first heat exchange module and the water inlet of the second heat exchange module, and the air outlet of the first heat exchange module is connected with the second air inlet of the second heat exchange module.
In a specific embodiment, a molten salt pump I4 is arranged between the molten salt outlet of the high-temperature molten salt tank 3 and the molten salt inlet of the first heat exchange module, and a molten salt pump II 6 is arranged between the molten salt outlet of the low-temperature molten salt tank 5 and the molten salt inlet of the solar heat collection tower 2.
In specific embodiments, the first heat exchange module comprises a superheater I12, an evaporator I11 and a preheater I10 which are sequentially connected, the molten salt inlet of the low-temperature molten salt tank 5 is connected with the molten salt outlet of the preheater I10, and the molten salt outlet of the high-temperature molten salt tank 3 is connected with the molten salt inlet of the superheater I12. The water is preheated to saturation temperature in the preheater I10, then is sent to the evaporator I11 for endothermic evaporation, and is sent to the superheater I12 for superheating after evaporation. The high-temperature molten salt sent out by the molten salt pump I4 sequentially passes through the superheater I12, the evaporator I11 and the preheater I10 to exchange heat with cold flow, and the high-temperature molten salt after heat exchange flows into the low-temperature molten salt tank 5.
In a specific embodiment, the second heat exchange module comprises a preheater II 13, an evaporator II 14, a superheater II 15 and a superheater III 17 which are sequentially connected, the water outlet of the water supply module is respectively connected with the water inlet of the preheater I10 and the water inlet of the preheater II 13, and the air outlet of the superheater I12 is connected with the second air inlet of the superheater III 17; the water is preheated to saturation temperature in the preheater II 13, then is sent into the evaporator II 14 for endothermic evaporation, and is sent into the superheater II 15 for superheating after evaporation.
In the specific embodiment, the cathode of the solid oxide electrolytic cell 19 is connected with the air outlet of the electric heater 18, and the superheated steam fed into the cathode generates hydrogen at the cathode and oxygen at the anode through electrochemical reaction. The high-temperature hydrogen discharged from the cathode outlet of the solid oxide electrolytic cell 19 and unreacted superheated steam and the high-temperature oxygen discharged from the anode outlet sequentially pass through a superheater III 17, a superheater II 15, an evaporator II 14, a preheater II 13 and a cold flow to exchange heat, and finally the high-temperature hydrogen and the unreacted superheated steam and the high-temperature oxygen are discharged from the anode outlet to be collected by a discharge system.
In a specific embodiment, the three-way confluence regulating valve 16 is further included, and the three-way confluence regulating valve 16 includes: the air inlet I is connected with the air outlet of the superheater I12, the air inlet II is connected with the air outlet of the superheater II 15, and the air outlet of the three-way confluence regulating valve 16 is connected with the second air inlet of the superheater III 17. The superheated steam from the superheater I12 is introduced into the air inlet I, the superheated steam from the superheater II 15 is introduced into the air inlet II, and is sent into the superheater III 17 from the air outlet after being converged, and the air outlet of the superheater III 17 is connected with the air inlet of the electric heater 18.
In a specific embodiment, the three-way split regulating valve 9 is further included, and the three-way split regulating valve 9 includes: the water outlet I is connected with the water inlet of the preheater I10, the water outlet II is connected with the water inlet of the preheater II 13, and the water inlet of the three-way shunt regulating valve 9 is connected with the water supply module.
In a specific embodiment, the water supply module comprises a water tank 7 and a water pump 8 connected.
In the specific embodiment, the solid oxide electrolytic cell 14 is connected with external direct current, direct current is introduced from the outside for electrolysis, and under different electric power input, the solid oxide electrolytic cell 14 has three working modes according to the magnitude relation of inlet and outlet temperatures: inputting first electric power, and working in an endothermic mode, wherein the temperature of a cathode air inlet of the solid oxide electrolytic cell 19 is higher than the temperatures of a cathode air outlet and an anode air outlet of the solid oxide electrolytic cell 19, and in the mode, the available heat of the cathode outlet gas and the anode outlet gas of the electrolytic cell is less, more electric heating cathode inlet superheated steam is needed, and the hydrogen production amount is minimum; inputting second electric power, and working in a thermal neutral mode, wherein the temperature of a cathode air inlet of the solid oxide electrolytic cell 19 is equal to the temperatures of a cathode air outlet and an anode air outlet of the solid oxide electrolytic cell 19, a small amount of electric heating cathode inlet superheated steam is required in the mode, and thermal stress is not generated in the electrolytic cell to influence the service life of the electrolytic cell; and the third electric power is input, and the solid oxide electrolytic cell 19 works in an exothermic mode, wherein the temperature of a cathode air inlet of the solid oxide electrolytic cell 19 is lower than the temperature of a cathode air outlet and an anode air outlet of the solid oxide electrolytic cell 19, and in the mode, the available heat of the cathode outlet gas and the anode outlet gas of the electrolytic cell is more, and the superheated steam at the cathode inlet is not required to be electrically heated in a certain temperature range.
The heat storage part of the system is double-tank direct heat storage, and molten salt in the high-temperature molten salt tank 3 and the low-temperature molten salt tank 5 is used as a heat transfer medium for heat exchange with cold flow and is also used as a heat storage medium. The heliostat field 1 condenses light and sends heat into the solar heat collection tower 2 to heat fused salt from the low-temperature fused salt tank 5, and the fused salt enters the high-temperature fused salt tank 3 for storage after being heated. And during electrolysis, high-temperature molten salt is output by a molten salt pump I4 and sequentially passes through a superheater I12, an evaporator I11 and a preheater I10 to exchange heat with cold flow for three times, cooled molten salt enters a low-temperature molten salt tank 5, and then is sent into a solar heat collection tower 2 by a molten salt pump II 6 to absorb heat and raise temperature to complete circulation.
The brine heat exchange process formed by the preheater I10, the evaporator I11 and the superheater I12 and the heat exchange process of the cathode and anode outlet heat flow and water of the solid oxide electrolytic cell 14 formed by the preheater II 13, the evaporator II 14 and the superheater II 15 are respectively carried out in parallel, at the initial stage of system start-up, the water outlet II of the three-way shunt regulating valve 9 is closed, the water sent by the water tank 7 through the water feed pump 8 is completely sent to the preheater I10, the evaporator I11 and the superheater I12 are subjected to three heat exchange with high-temperature molten salt to become superheated steam, and then the superheated steam is sent to the electric heater 18 through the three-way confluence regulating valve 16 and the superheater III 17 in sequence to be heated to the temperature required by electrolysis, and then enters the solid oxide electrolytic cell 19 to be electrolyzed; along with the progress of the electrolysis reaction, after the heat flows at the cathode and anode outlets of the solid oxide electrolytic cell 14 are stably output, the water outlet II of the three-way shunt regulating valve 9 is opened, the shunt of the water outlet I and the water outlet II is regulated to a proper proportion, and the mass flow of the high-temperature molten salt is regulated through the molten salt pump I4, so that the heat exchange can be carried out with cold flow respectively by utilizing a parallel structure formed by the heat flow of the high-temperature molten salt and the heat flows at the cathode and anode outlets of the solid oxide electrolytic cell 14.
In a specific embodiment, the solid oxide electrolytic cell 19 adopts a conventional solid oxide electrolytic cell, the anode material is Ni-YSZ, the electrolyte material is YSZ, the cathode material is LSM-YSZ, the effective area of a single electrolytic cell is 127cm < 2 >, 200 electrolytic cells form an electrolytic cell stack, the embodiment comprises 6 electrolytic cell stacks in total, the electric power input into the solid oxide electrolytic cell 19 is controlled to work in a thermal neutral mode, and the inlet high-temperature steam temperature is equal to the outlet exhaust temperature and is 800 ℃.
In a specific embodiment, the heat storage part of the system is double-tank direct heat storage, and the molten salts in the high-temperature molten Salt tank 3 and the low-temperature molten Salt tank 5 adopt Solar Salt (60% NaNO3+40% KNO 3) composite molten Salt which is used as a heat transfer medium and a heat storage medium. The heliostat field 1 condenses light and sends heat into the solar heat collection tower 2 to heat molten salt from the low-temperature molten salt tank 5, and the molten salt is heated to 565 ℃ and then enters the high-temperature molten salt tank 3 for storage. And during electrolysis, high-temperature molten salt is output by a molten salt pump I4 and sequentially passes through a superheater I12, an evaporator I11 and a preheater I10 to exchange heat with cold flow for three times, and cooled molten salt enters a low-temperature molten salt tank 5 and is sent into a solar heat collection tower 2 by a molten salt pump II 6 to absorb heat and raise temperature to complete circulation.
The working principle is as follows:
At the initial stage of system starting, a water outlet II of a three-way shunt regulating valve 9 is closed, water sent by a water tank 7 through a water feeding pump 8 is completely sent to a preheater I10, heat exchange is carried out on the water and high-temperature molten salt in the preheater I10, an evaporator I11 and a superheater I12 for three times to form superheated steam, and the superheated steam is sent to an electric heater 18 through a three-way confluence regulating valve 16 and a superheater III 17 in sequence to be heated to the temperature required by electrolysis, and then enters a solid oxide electrolytic cell 19 for electrolysis;
After the heat flows at the outlets of the cathode and anode of the solid oxide electrolytic cell 19 are stably output, the mass flow of the high-temperature molten salt is regulated through a molten salt pump I4, the water outlet II of a three-way shunt regulating valve 9 is opened, water fed from a water tank 7 is used as cold flow to be shunted according to a proper proportion through the three-way shunt regulating valve 9, one cold flow after being shunted enters a molten salt heat storage type solar photo-thermal module, three heat exchange is carried out with the high-temperature molten salt through a preheater I10, an evaporator I11 and a superheater I12 in sequence, the other cold flow sequentially carries out three heat exchange with the heat flows at the outlets of the cathode and anode of the solid oxide electrolytic cell 19 through a preheater II 13, an evaporator II 14 and a superheater II 15, the two cold flows respectively achieve the same temperature level after the two cold flows are preheated, evaporated and overheated, the three-way confluence regulating valve 16 is used for confluence, then the gas heat at the outlets of the cathode and anode of the solid oxide electrolytic cell is absorbed by a superheater III 17, the solid oxide electrolytic cell is carried out again, and finally the solid oxide electrolytic cell 19 is heated by an electric heater 18 to reach the electrolysis temperature, and hydrogen and oxygen are generated. The high-temperature hydrogen discharged from the cathode, unreacted superheated steam and high-temperature oxygen discharged from the anode are sequentially sent into a superheater III 17, a superheater II 15, an evaporator II 14, a preheater II 13 and cold flow for heat exchange, and finally discharged from the system for collection.
When water under standard conditions is fed into the system through the water feed pump 8 at a flow rate of 0.01800kg/s, at the initial stage of system start-up, the water outlet II of the three-way shunt regulating valve 9 is closed, all water fed out from the water tank 7 through the water feed pump 8 is fed into the preheater I10, the high-temperature molten salt which is output by the high-temperature molten salt tank 3 in the preheater I10, the evaporator I11 and the superheater I12 is subjected to three heat exchange with 565 ℃ and 0.15115kg/s of high-temperature molten salt to become 550 ℃ superheated steam, and then the superheated steam is fed into the electric heater 18 through the three-way shunt regulating valve 16 and the superheater III 17 in sequence to be heated to 800 ℃ and then enters the solid oxide electrolytic cell 19 for electrolysis.
After the heat flows at the outlets of the cathode and the anode of the solid oxide electrolytic cell 14 are stably output, the mass flow of high-temperature molten salt is regulated to 0.10241kg/s through a molten salt pump I4, a water outlet II of a three-way shunt regulating valve 9 is opened, water is shunted through the three-way shunt regulating valve 9, 0.01235kg/s of water sequentially passes through a preheater I10, an evaporator I11 and a superheater I12 to exchange heat with the high-temperature molten salt for three times, the other water sequentially passes through the preheater II 13, the evaporator II 14 and the superheater II 15 at a flow rate of 0.00565kg/s to exchange heat with the heat flows at the outlets of the cathode and the anode of the solid oxide electrolytic cell 19 for three times, then the three-way confluence regulating valve 16 is used for confluence, the heat flows into the superheater III 17 to absorb the heat of the gas at the outlets of the cathode and the anode of the solid oxide electrolytic cell to reach 790 ℃ again, finally the electric heater is heated to 800 ℃, the solid oxide electrolytic cell 14 is electrolyzed under 160kW of electric power, the exhaust temperature of the cathode and the anode is 800 ℃, the hydrogen yield of the cathode is 0.01032kg/s, the oxygen yield of the anode is 0.01032kg/s, the total heat flows into a cooling system of 3525% after the temperature of the molten salt is controlled to be discharged from the preheater 13, the total heat flows into a cooling system of the cooling system of low temperature of 3525%, and the total heat efficiency is stable after the heat is cooled down to the system of the heat is discharged to be at the temperature of 3525%.
The components not described in detail in this embodiment are all existing components that can be purchased in public channels.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. A tower solar photo-thermal coupling solid oxide water electrolysis hydrogen-producing heat system, comprising: the system comprises a fused salt heat storage type tower solar photo-thermal module, a first heat exchange module, a second heat exchange module, a solid oxide electrolyzed water hydrogen production module and a water supply module;
The fused salt heat storage type tower solar photo-thermal module is used for heat collection and heat storage and comprises: the solar energy heat collection system comprises a heliostat field (1), a solar energy heat collection tower (2), a high-temperature molten salt tank (3) and a low-temperature molten salt tank (5); the heliostat field (1) reflects sunlight to the solar heat collection tower (2) to collect heat and heat molten salt, a molten salt outlet of the solar heat collection tower (2) is connected with a molten salt inlet of the high-temperature molten salt tank (3), and a molten salt outlet of the low-temperature molten salt tank (5) is connected with a molten salt inlet of the solar heat collection tower (2);
The molten salt outlet of the high-temperature molten salt tank (3) is connected with the molten salt inlet of the first heat exchange module, and the molten salt inlet of the low-temperature molten salt tank (5) is connected with the molten salt outlet of the first heat exchange module;
the solid oxide water electrolysis hydrogen production module comprises: the solid oxide electrolytic cell comprises an electric heater (18) and a solid oxide electrolytic cell (19), wherein a cathode air inlet of the solid oxide electrolytic cell (19) is connected with an air outlet of the electric heater (18); the cathode air outlet and the anode air outlet of the solid oxide electrolytic cell (19) are connected with the first air inlet of the second heat exchange module; the first air outlet of the second heat exchange module is connected with the air inlet of the electric heater (18), and the second air outlet of the second heat exchange module is connected with the outside of the system;
the water outlet of the water supply module is respectively connected with the water inlet of the first heat exchange module and the water inlet of the second heat exchange module, and the air outlet of the first heat exchange module is connected with the second air inlet of the second heat exchange module.
2. The tower type solar photo-thermal coupling solid oxide water electrolysis hydrogen production heat system according to claim 1 is characterized in that a molten salt pump I (4) is arranged between a molten salt outlet of the high-temperature molten salt tank (3) and a molten salt inlet of the first heat exchange module, and a molten salt pump II (6) is arranged between a molten salt outlet of the low-temperature molten salt tank (5) and a molten salt inlet of the solar heat collection tower (2).
3. The tower type solar photo-thermal coupling solid oxide water electrolysis hydrogen production heat system according to claim 1, wherein the first heat exchange module comprises a superheater I (12), an evaporator I (11) and a preheater I (10) which are sequentially connected, a molten salt inlet of the low-temperature molten salt tank (5) is connected with a molten salt outlet of the preheater I (10), and a molten salt outlet of the high-temperature molten salt tank (3) is connected with a molten salt inlet of the superheater I (12).
4. A tower solar photo-thermal coupling solid oxide water electrolysis hydrogen production heat system according to claim 3, wherein the second heat exchange module comprises a preheater II (13), an evaporator II (14), a superheater II (15) and a superheater III (17) which are sequentially connected, the water outlet of the water supply module is respectively connected with the water inlet of the preheater I (10) and the water inlet of the preheater II (13), and the air outlet of the superheater I (12) is connected with the second air inlet of the superheater III (17).
5. The tower type solar photo-thermal coupling solid oxide water electrolysis hydrogen production heat system according to claim 4, wherein high-temperature hydrogen discharged from a cathode outlet of the solid oxide electrolytic cell (19) and unreacted superheated steam and high-temperature oxygen discharged from an anode outlet sequentially pass through the superheater III (17), the superheater II (15), the evaporator II (14), the preheater II (13) and cold flow to exchange heat, and finally the high-temperature hydrogen and the high-temperature oxygen are discharged from the anode outlet to be collected.
6. The tower solar photo-thermal coupling solid oxide water electrolysis hydrogen production thermal system according to claim 4, further comprising a three-way confluence regulating valve (16), wherein the three-way confluence regulating valve (16) comprises: the air inlet I is connected with an air outlet of the superheater I (12), the air inlet II is connected with an air outlet of the superheater II (15), and an air outlet of the three-way converging regulating valve (16) is connected with a second air inlet of the superheater III (17).
7. The tower solar photo-thermal coupling solid oxide water electrolysis hydrogen production thermal system according to claim 4, further comprising a three-way shunt regulator valve (9), the three-way shunt regulator valve (9) comprising: the water inlet of the three-way shunt regulating valve (9) is connected with the water supply module.
8. The tower type solar photo-thermal coupling solid oxide water electrolysis hydrogen production and heating system according to claim 1, wherein the water supply module comprises a water tank (7) and a water pump (8) which are connected.
9. The tower type solar photo-thermal coupling solid oxide water electrolysis hydrogen production heat system according to claim 1, wherein the solid oxide electrolysis cell (14) is connected with external direct current, and the direct current is introduced from the outside for electrolysis.
10. The tower type solar photo-thermal coupling solid oxide water electrolysis hydrogen production heat system according to claim 9, wherein under different electric power input, the solid oxide electrolysis cell (14) has three working modes according to the magnitude relation of inlet and outlet temperatures: inputting first electric power, and working in an endothermic mode, wherein the temperature of a cathode air inlet of the solid oxide electrolytic cell (19) is higher than the temperatures of a cathode air outlet and an anode air outlet of the solid oxide electrolytic cell (19), and in the mode, the available heat of the cathode outlet gas and the anode outlet gas of the electrolytic cell is less, more electric heating cathode inlet superheated steam is needed, and the hydrogen production amount is minimum; inputting second electric power, and working in a thermal neutral mode, wherein the temperature of a cathode air inlet of the solid oxide electrolytic cell (19) is equal to the temperatures of a cathode air outlet and an anode air outlet of the solid oxide electrolytic cell (19), a small amount of electric heating cathode inlet superheated steam is required in the mode, and thermal stress is not generated in the electrolytic cell to influence the service life of the electrolytic cell;
And the third electric power is input, the operation is in an exothermic mode, the temperature of a cathode air inlet of the solid oxide electrolytic cell (19) is lower than the temperatures of a cathode air outlet and an anode air outlet of the solid oxide electrolytic cell (19), and in the mode, the available heat of the cathode outlet gas and the anode outlet gas of the electrolytic cell is more, and the overheating steam of the cathode inlet is not required to be electrically heated in a certain temperature range.
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