CN113322475B - High-temperature solid oxide water electrolysis hydrogen production system and process coupling solar energy amino-thermal chemical energy storage and kalina circulation - Google Patents
High-temperature solid oxide water electrolysis hydrogen production system and process coupling solar energy amino-thermal chemical energy storage and kalina circulation Download PDFInfo
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- F03G6/00—Devices for producing mechanical power from solar energy
- F03G6/06—Devices for producing mechanical power from solar energy with solar energy concentrating means
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
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- F24S10/30—Solar heat collectors using working fluids with means for exchanging heat between two or more working fluids
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S60/00—Arrangements for storing heat collected by solar heat collectors
- F24S60/20—Arrangements for storing heat collected by solar heat collectors using chemical reactions, e.g. thermochemical reactions or isomerisation reactions
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/40—Solar thermal energy, e.g. solar towers
- Y02E10/44—Heat exchange systems
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/40—Solar thermal energy, e.g. solar towers
- Y02E10/46—Conversion of thermal power into mechanical power, e.g. Rankine, Stirling or solar thermal engines
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- 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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- 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
Abstract
The invention discloses a high-temperature solid oxide water electrolysis hydrogen production system and process for coupling solar energy amino thermochemical energy storage and kalina circulation. The invention can reduce the cost of light condensation and heat collection, reduce the energy storage loss, and improve the power generation cycle efficiency and the hydrogen production efficiency by reducing the energy absorption grade, storing at normal temperature and improving the energy release grade.
Description
Technical Field
The invention belongs to the technical field of hydrogen production by electrolyzing water by solar energy, and particularly relates to a high-temperature solid oxide hydrogen production system by electrolyzing water by coupling solar energy based on amino thermochemical energy storage and kalina circulation and a process thereof.
Background
Solar energy, being the largest scale renewable energy source, can reduce human dependence on fossil energy and carbon emissions. In order to overcome the intermittent deficiency of solar energy, the solar energy can be stored in fuel, such as hydrogen, methanol and other transportable energy carriers, wherein the hydrogen has the advantages of high energy density, no pollution and the like, and is considered to be one of the best secondary energy sources. Therefore, solar hydrogen production is one of the important solutions to achieve carbon neutralization early.
Because the condensation pressure of ammonia water vapor is far higher than that of water vapor under the same condensation temperature, the steam exhaust of the kalina cycle works in a state of being higher than atmospheric pressure, thereby avoiding a plurality of troubles caused by vacuum in the traditional water vapor cycle. The kalina cycle can adapt to the change of ambient temperature by adjusting the concentration of the mixed solution, so that the low-temperature environment in winter is fully utilized, more output is obtained, and the concern of icing of the working medium is avoided. Similarly, the kalina cycle can maintain efficiency at steady levels by varying the solution concentration as the load varies.
The high-temperature solid oxide electrolytic cell is an efficient and low-pollution energy conversion device, can convert electric energy and heat energy into chemical energy, thereby realizing the purpose of efficiently producing hydrogen and storing energy, and greatly relieving energy crisis and environmental deterioration. Compared with the conventional water electrolysis, the method for producing hydrogen by electrolyzing water vapor at the high temperature by utilizing SOEC has the advantages of higher efficiency, environmental friendliness and the like, and can be combined with various clean energy sources to be used for preparing hydrogen, oxygen and other energy carriers. The SOEC is mainly composed of ceramic materials, does not need noble metals, has lower material cost, and does not have the corrosion problem of the conventional alkaline electrolysis. The ceramic material has better mechanical strength, and if the ceramic material operates under higher pressure, the hydrogen production efficiency can be further improved. In addition, the scale and the working temperature of the hydrogen production by the water vapor electrolysis of the high-temperature solid oxide can be flexibly adjusted according to different heat energy sources. Although the conventional solar photo-thermal power generation utilizes a heat collection system with a higher concentration ratio and a sensible heat energy storage system with a higher working temperature to heat water to the temperature (above 700 ℃) required by the HTE, high-temperature concentration and heat storage cause a great amount of energy loss and result in a sharp increase in the cost of hydrogen production.
The amino thermochemical energy storage system stores energy through conversion of heat energy and chemical energy. NH (NH)3The system has the unique advantages that other thermochemical or photochemical energy storage materials do not have, such as high energy storage density, easy control of reversible reaction, no side reaction, mature technology, reliable application, simple storage and separation and the like, besides the advantages of abundant and cheap raw materials and all-weather continuous energy supply, the system becomes a preferred thermochemical energy storage substance for solar thermal power generation. The experimental research of utilizing ammonia decomposition reaction as solar energy for heat storage and power generation is carried out abroad, the efficiency is more than 0.6, and therefore, the reaction still has practical prospect. The amino thermochemical energy storage system is simple and miniaturized, can effectively collect, store, convey and convert solar energy without worrying about the transient property of solar radiation, and the energy generated by the synthesis reaction is high in quality, but NH3/N2/H2In the actual application of the thermochemical energy storage system, some problems still need to be solved, for example, the reaction is operated under high temperature, high pressure and catalyst, the reaction conditions are harsh, and the operating cost of the energy storage system is high; incomplete conversion of the reaction, etc.
For the hydrogen production mode, about 50% comes from steam reforming of natural gas, 30% comes from heavy oil reforming, and 18% comes from gasification of coal. When hydrogen is used as an energy source, the demand of the hydrogen is large, and a green and economic hydrogen production method must be sought. The thermochemical hydrogen production has great practical significance, but the thermochemical hydrogen production is a very difficult research subject and has a large number of theoretical problems and engineering technical problems to be solved. At present, the research on large-scale solar hydrogen production mainly focuses on solar photovoltaic water electrolysis and solar photo-thermal hydrogen production. Although the solar photovoltaic electrolyzed water can reach the solar hydrogen production efficiency of more than 30 percent, the solar photovoltaic electrolyzed water has the defects of intermittence, instability and the like, so that the installed capacity is larger than the actual operation power, and the cost is increased.
Disclosure of Invention
The invention aims to provide a high-temperature solid oxide water electrolysis hydrogen production system and process for coupling solar amino thermochemical energy storage and kalina circulation.
In order to achieve the purpose, the following technical scheme is provided:
the high-temperature solid oxide water electrolysis hydrogen production system is characterized by comprising an amino thermal chemical energy storage system, a kalina circulation system and a high-temperature solid oxide water electrolysis hydrogen production system, wherein the amino thermal chemical energy storage system and the high-temperature solid oxide water electrolysis hydrogen production system are in heat exchange connection through a sixth heat exchanger, a third heat exchanger and a seventh heat exchanger, the amino thermal chemical energy storage system and the kalina circulation system are in heat exchange connection through a fifth heat exchanger, and the kalina circulation system is connected with the high-temperature solid oxide water electrolysis hydrogen production system to provide raw materials for the high-temperature solid oxide water electrolysis hydrogen production system.
Further, the amino-thermal chemical energy system comprises a heliostat field, an endothermic reactor, a first heat exchanger, a normal-temperature pressure storage tank, a second heat exchanger, a third heat exchanger, an adiabatic reactor, a fifth heat exchanger and a seventh heat exchanger, wherein the endothermic reactor, the first heat exchanger and the normal-temperature pressure storage tank form a circulation loop through a first gas pipe and a first liquid pipe, the second gas pipe is sequentially connected with the normal-temperature pressure storage tank, the second heat exchanger, the third heat exchanger and the adiabatic reactor, an outlet of the adiabatic reactor is divided into a second liquid pipe, a first pipeline and a second pipeline, the second liquid pipe is sequentially connected with the fifth heat exchanger, the second heat exchanger and the normal-temperature pressure storage tank, the second gas pipe and the second liquid pipe form a circulation loop, the first pipeline is connected with an inlet of the sixth heat exchanger, and an outlet of the first pipeline is connected with a pipeline between the second heat exchanger and the fifth heat exchanger in a converging manner, the second pipeline is connected with the inlet of the seventh heat exchanger, the outlet of the second pipeline is connected with the pipeline between the second heat exchanger and the fifth heat exchanger in a converging manner, and the fifth heat exchanger is connected with the kalina circulating system.
Further, the kalina circulation system comprises a fifth heat exchanger, a generator, an eighth heat exchanger, an absorber, a solution pump and a turbine, wherein a circulation loop is formed among the generator, the eighth heat exchanger and the absorber through two pipelines, the pipeline of an outlet at the lower end of the absorber in the circulation loop is connected with the solution pump, an outlet of the solution pump is connected with the eighth heat exchanger through a pipeline, the absorber, the fifth heat exchanger and the generator are sequentially connected, an outlet at the upper end of the generator is connected with the turbine, the turbine is connected with the absorber, and the generator is connected with the high-temperature solid oxide water electrolysis hydrogen production system.
Further, the high-temperature solid oxide water electrolysis hydrogen production system comprises a high-temperature solid oxide electrolytic cell, a ninth heat exchanger, a tenth heat exchanger, a separator, a third heat exchanger, a fourth heat exchanger, a sixth heat exchanger and a seventh heat exchanger, wherein a cathode inlet of the high-temperature solid oxide electrolytic cell is connected with the generator through a third pipeline, a cathode outlet of the high-temperature solid oxide electrolytic cell is connected with the ninth heat exchanger, the tenth heat exchanger and the separator are sequentially connected to form a circulation loop, an outlet of the ninth heat exchanger is connected with an inlet of the sixth heat exchanger, an outlet of the sixth heat exchanger is connected with a third pipeline in a converging manner through a pipeline, an outlet of the seventh heat exchanger is connected with an anode inlet of the high-temperature solid oxide electrolytic cell, and an outlet of the seventh heat exchanger is connected with the fourth heat exchanger through the third heat exchanger.
Furthermore, a throttle valve is arranged on a pipeline connecting the absorber and the eighth heat exchanger.
A process for producing hydrogen by adopting a high-temperature solid oxide water electrolysis hydrogen production system which couples solar energy amino thermochemical energy storage and kalina circulation comprises the following steps: the heliostat field reflects sunlight to the endothermic reactor, ammonia water solution in a normal temperature state flows out from an outlet at the bottom of the normal temperature pressure storage tank, enters the first heat exchanger along a first liquid conveying pipe for heat exchange and temperature rise, then enters the endothermic reactor along the first liquid conveying pipe for ammonia decomposition reaction, generated mixed gas enters the first heat exchanger along a first gas conveying pipe for heat exchange, and finally flows into the endothermic reactor from an inlet at the bottom of the normal temperature pressure storage tank for storage to form a circulation loop; the reaction gas flows out from the outlet at the top of the normal temperature pressure storage tank and sequentially passes through the second heat exchanger and the third heat exchanger along the second gas transmission pipe to exchange gasHeating, then entering an adiabatic reactor to perform ammonia synthesis reaction, sequentially exchanging heat of the ammonia generated by the reaction through a fifth heat exchanger and a second heat exchanger along a second liquid conveying pipe, and finally entering and storing from an inlet at the top of a normal-temperature pressure storage tank to form a circulation process; an ammonia water solution circulation loop is formed between the generator and the absorber, a strong ammonia solution from the absorber enters an eighth heat exchanger through a solution pump in a pressurizing mode, a part of energy is recycled and then enters the generator, ammonia vapor containing a small amount of water vapor enters a turbine from a gas outlet in the top of the generator to do work to generate electric power, low-pressure and low-temperature ammonia vapor after power generation enters the absorber and is absorbed by a dilute solution from the generator, the released heat is taken away by cooling water, and the dilute ammonia water solution from the generator enters the absorber after passing through the eighth heat exchanger to form a circulation process; cooling water firstly enters an absorber to absorb heat and raise temperature, then enters a fifth heat exchanger to further absorb heat and raise temperature, finally high-temperature water vapor enters an ammonia water solution in a heating generator of the generator, the water vapor after the ammonia water solution in the heating generator is discharged from a water outlet at the bottom of the generator and enters a cathode of a high-temperature solid oxide electrolytic cell along a third pipeline to serve as an electrolytic raw material, and a cathode product H2And H2The O enters a ninth heat exchanger for heat exchange and then enters a tenth heat exchanger for cold extraction to a standard state, water and hydrogen are separated in a separator, and the separated H2Discharging from the top of the separator to obtain H2The separated water firstly enters a ninth heat exchanger to absorb heat and raise the temperature, then enters a sixth heat exchanger to further absorb heat and raise the temperature, finally enters the cathode of the high-temperature solid oxide electrolytic cell along a third pipeline to participate in circulation, and air enters a seventh heat exchanger to raise the temperature and then enters the high-temperature solid oxide electrolytic cell to purge an anode product O2，O2Firstly enters a third heat exchanger for heat exchange, then enters a fourth heat exchanger for cooling to a standard state and is discharged to obtain O2And (5) producing the product.
Further, the working temperature range of the high-temperature solid oxide electrolytic cell is 650-850 ℃, and the temperature range of the separator is 20-30 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1) the high-temperature solid oxide water electrolysis hydrogen production system coupling solar energy amino-thermal chemical energy storage and kalina circulation can reduce light-gathering and heat-collecting cost, reduce energy storage loss and improve power generation circulation efficiency and water electrolysis hydrogen production efficiency by reducing energy absorption grade, storing at normal temperature and improving energy release grade.
2) The invention provides a novel method for preparing hydrogen by electrolyzing water by high-temperature solid oxide by coupling solar energy amino thermochemical energy storage and kalina circulation, which adopts an amino solar thermochemical energy storage system as an energy storage module, and has the advantages that a chemical heat pump is used for reducing the temperature of an energy absorption side, reducing the energy loss, improving the temperature of energy release measurement and improving the energy efficiency of a subsequent system; meanwhile, the system can run all weather through the energy storage module, and the intermittent running of the photovoltaic hydrogen production system is overcome.
3) The coupling system is simple and miniaturized, can effectively collect, store, convey and convert solar energy without worrying about the transient property of solar radiation, has high energy quality generated by synthetic reaction, has rich and cheap raw materials for removing amino system, can continuously supply energy in all weather, can be used for SOEC electrolysis of surplus electric energy of kalina cycle power generation system, and is expected to further reduce the hydrogen production cost.
Drawings
FIG. 1 is a process flow diagram of the present invention;
in the figure: 1-a heliostat field; 2-endothermic reactor; 3-a first heat exchanger; 4-normal temperature pressure storage tank; 5-a second heat exchanger; 6-a third heat exchanger; 7-a fourth heat exchanger; 8-adiabatic reactor; 9-a fifth heat exchanger; 10-a sixth heat exchanger; 11-a seventh heat exchanger; 12-a generator; 13-a throttle valve; 14-a turbine; 15-an absorber; 16-an eighth heat exchanger; 17-a solution pump; 18-high temperature solid oxide electrolytic cell; 19-a ninth heat exchanger; 20-a tenth heat exchanger; 21-a separator; 22-a first gas line; 23-a first infusion tube; 24-a second gas delivery conduit; 25-a second infusion tube; 26-a first conduit; 27-a second conduit; 28-third line.
Detailed Description
The present invention is described in further detail below with reference to the drawings and examples of the specification, and the following examples or drawings are used to illustrate the present invention but are not intended to limit the scope of the present invention.
Referring to fig. 1, a high-temperature solid oxide water electrolysis hydrogen production system coupling solar amino thermochemical energy storage and kalina circulation comprises an amino thermochemical energy storage system, a kalina circulation system and a high-temperature solid oxide water electrolysis hydrogen production system;
the amino thermal chemical energy storage system comprises a heliostat field 1, an endothermic reactor 2, a first heat exchanger 3, a normal-temperature pressure storage tank 4, a second heat exchanger 5, a third heat exchanger 6, an adiabatic reactor 8, a fifth heat exchanger 9, a sixth heat exchanger 10 and a seventh heat exchanger 11; the endothermic reactor 2, the first heat exchanger 3 and the normal temperature pressure storage tank 4 are connected in sequence through a first gas pipe 22 and a first liquid pipe 23 to form a circulation loop, the normal temperature pressure storage tank 4, the second heat exchanger 5, the third heat exchanger 6 and the adiabatic reactor 8 are connected in sequence through a second gas pipe 24, and the adiabatic reactor 8, the fifth heat exchanger 9, the second heat exchanger 5 and the normal temperature pressure storage tank 4 are connected in sequence through a second liquid pipe 25; the outlet of the adiabatic reactor 8 is divided into two paths, one path is connected to the hot end inlet of the sixth heat exchanger 10 through a first pipeline 26, the corresponding outlet of the sixth heat exchanger is connected with the pipeline between the fifth heat exchanger 9 and the second heat exchanger 5 in a converging manner, the other path is further divided into two paths, one path is connected to the hot end inlet of the fifth heat exchanger 9 through a second infusion tube 25, one path is connected to the hot end inlet of the seventh heat exchanger 11 through a second pipeline 27, and the corresponding outlet of the fifth heat exchanger is connected with the pipeline between the fifth heat exchanger 9 and the second heat exchanger 5 in a converging manner.
The kalina circulating system comprises a fifth heat exchanger 9, a generator 12, a turbine 14, an absorber 15, a throttle valve 13, a solution pump 17 and an eighth heat exchanger 16; the outlet of the cold end of the fifth heat exchanger 9 is connected with the water inlet of the generator 12, the inlet of the cold end of the fifth heat exchanger 9 is connected with the water outlet of the absorber 15, the water outlet of the generator 12 is connected with the water inlet of the high-temperature solid oxide electrolytic cell 18 through a third pipeline 28, the gas outlet of the top of the generator 12 is connected with the inlet of the turbine 14, the outlet of the turbine 14 is connected with the gas inlet of the top of the absorber 15, the liquid outlet of the bottom of the absorber 15 is connected with the inlet of the solution pump 17, the outlet of the solution pump 17 is connected with the inlet of the cold end of the eighth heat exchanger 16, the outlet of the cold end of the eighth heat exchanger 16 is connected with the liquid inlet of the top of the generator 12, the liquid outlet of the bottom of the generator 12 is connected with the hot end inlet of the eighth heat exchanger 16, the hot end outlet of the eighth heat exchanger 16 is connected with the inlet of the throttle valve 13, and the outlet of the throttle valve 13 is connected with the liquid inlet of the top of the absorber 15.
The high-temperature solid oxide water electrolysis hydrogen production system comprises a high-temperature solid oxide electrolytic cell 18, a ninth heat exchanger 19, a tenth heat exchanger 20, a separator 21, a third heat exchanger 6, a fourth heat exchanger 7, a sixth heat exchanger 10 and a seventh heat exchanger 11; the cathode outlet of the high-temperature solid oxide electrolytic cell 18 is connected with the hot end inlet of the ninth heat exchanger 19, the hot end outlet of the ninth heat exchanger 19 is connected with the inlet of the tenth heat exchanger 20, the outlet of the tenth heat exchanger 20 is connected with the inlet at the bottom of the separator 21, the outlet at the bottom of the separator 21 is connected with the cold end inlet of the ninth heat exchanger 19, the cold end outlet of the ninth heat exchanger 19 is connected with the cold end inlet of the sixth heat exchanger 10, the cold end outlet of the sixth heat exchanger 10 is connected with the third pipeline 28 in a converging manner, the anode inlet of the high-temperature solid oxide electrolytic cell 18 is connected with the cold end inlet of the seventh heat exchanger 11, the outlet is connected with the hot end inlet of the third heat exchanger 6, and the hot end outlet of the third heat exchanger 6 is connected with the inlet of the fourth heat exchanger 7.
Example 1
The intensity of solar radiation light is 1000W/m2The light condensation ratio is 200, the light is reflected to an endothermic reactor 2 (the inner diameter is 6.2mm, the outer diameter is 8.7mm, the length is 1220 mm) through a heliostat field 1, the reactor material is made of Inconel625, nickel-based catalyst particles are filled in the reactor, the diameter of the catalyst particles is 0.4-0.6mm, the endothermic reactor 2 is enabled to reach 800 ℃, firstly, liquid ammonia with the temperature of 25 ℃ and the pressure of 30MPa flows out from a liquid outlet at the bottom of a normal-temperature pressure storage tank 4, enters a first heat exchanger 3 for heat exchange and temperature rise to 400 ℃, and then flows into the endothermic reactor 2 for ammonia decomposition reaction (2 NH)3→3H2+N2) Synthesis gas (H) produced2+N2) Flows out from the outlet and enters the first heat exchanger 3, the heat exchange temperature is 28 ℃, then enters the normal temperature pressure storage tank 4 from the bottom air inlet and is stored, and the synthesis gas (the temperature is 25 ℃, the flow is 4.182 g/s) stored in the normal temperature pressure storage tank 4 is discharged from the topThe gas outlet flows out to enter a second heat exchanger 5 for heat exchange and temperature rise to 250 ℃, enters a third heat exchanger 6 for heat exchange and temperature rise to 500 ℃, enters an adiabatic reactor 8 (a tubular fixed bed reactor, the length of the reactor is 1100 mm) to generate a synthetic ammonia reaction (3H)2+N2→2NH3) The reaction releases heat to raise the temperature to 800 ℃, ammonia steam flows out from an outlet and is divided into two paths, and a first pipeline 26 enters the sixth heat exchanger 10 and mixed gas (15% H) from the ninth heat exchanger 192+85%H2O) heat exchange, the mixed gas is heated to 720 ℃ and then mixed and flows into a third pipeline 28; the second liquid conveying pipe 25 is divided into two branches, one branch of the second pipeline 27 enters the seventh heat exchanger 11 to heat the air to 700 ℃, and then enters the high-temperature solid oxide electrolytic cell 18 to purge O2(ii) a The other branch enters a fifth heat exchanger 9 to exchange heat with the water vapor from an absorber 15 so that the temperature of the water vapor is increased to 740 ℃, the ammonia gas after heat exchange is converged with the ammonia gas of a sixth heat exchanger 10 and a seventh heat exchanger 11 to enter a second heat exchanger 5 to exchange heat, and the ammonia gas enters a normal-temperature pressure storage tank 4 to be stored when the temperature reaches 25 ℃.
70% concentrated ammonia solution from a liquid outlet at the bottom of the absorber 15 is pressurized by a solution pump 17 to enter an eighth heat exchanger 16, part of energy is recovered and then enters the generator 12, after high-temperature steam from the fifth heat exchanger 9 exchanges heat, ammonia steam containing a small amount of steam enters a turbine 14 from a gas outlet at the top of the generator 12 to do work to generate electric power, the generated low-pressure and low-temperature ammonia steam with the pressure of 0.059MPa and the temperature of 255 ℃ enters the absorber 15 and is absorbed by 45% dilute solution from a liquid outlet at the bottom of the generator 12 in the absorber 15, and the released heat is taken away by cooling water with the temperature of 15 ℃. Cooling water enters from a water inlet at the bottom of the absorber 15 for heat exchange and then is heated to 330 ℃, then enters the fifth heat exchanger 9 for heat exchange and is heated to 740 ℃, then enters the generator 12 from a water inlet at the bottom of the generator 12, water vapor after heating the ammonia water solution in the generator 12 is discharged from a water outlet at the bottom of the generator 12, the temperature is 720 ℃, the flow rate is 1.65kg/h, and the water vapor enters the high-temperature solid oxide electrolytic cell 18 along the third pipeline 28 and enters the cathode of the electrolytic cell to serve as an electrolytic raw material.
Hydrolysis reaction takes place in the high temperature solid oxide electrolytic cell 18, the cathode portion (H)2O+2e-→H2+O2-) Obtaining the cathode product (H)2、H2O), the temperature of the mixed gas is 700 ℃, the pressure is 0.28MPa, the flow is 0.67kg/H, the mixed gas firstly enters a ninth heat exchanger 19 for heat exchange, then enters a tenth heat exchanger 20 for cold extraction to the normal temperature of 25 ℃, water and hydrogen are separated in a separator 21, and the separated H2Discharging from the top of separator 21 to obtain H2Producing a product; separated normal temperature water and a small amount of H2（15%H2+85%H2O) enters the ninth heat exchanger 19 for heat exchange and temperature rise, then enters the sixth heat exchanger 10 for temperature rise to 720 ℃, and finally enters the third pipeline 28 for circulation; o generation at the anode portion of the high temperature solid oxide electrolytic cell 182-→2e-+1/2O2The inlet material temperature is 25 ℃, the air with the flow rate of 3.88kg/h enters the seventh heat exchanger 11 to be heated to 700 ℃, and then enters the high-temperature solid oxide electrolytic cell 18 to purge the anode product (O) with the temperature of 700 ℃, the pressure of 0.28MPa and the flow rate of 4.55kg/h2），O2Firstly enters a third heat exchanger 6 for heat exchange, then enters a fourth heat exchanger 7 for cooling to the normal temperature of 25 ℃ and is discharged to obtain O2And (5) producing the product.
Example 2
The intensity of solar radiation light is 1000W/m2The light concentration ratio was 200, and the light was reflected by a heliostat field 1 to an endothermic reactor 2 (inner diameter 6.2mm, outer diameter 8.7mm, length 1220mm, reactor material made of Inconel625, nickel-based catalyst particles having a diameter of 0.4 to 0.6mm filled inside the reactor) to reach 800 ℃. Firstly, liquid ammonia with the temperature of 25 ℃ and the pressure of 30MPa flows out from a liquid outlet at the bottom of a normal-temperature pressure storage tank 4, enters a first heat exchanger 3 for heat exchange, is heated to 400 ℃, and then flows into an endothermic reactor 2 for ammonia decomposition reaction (2 NH)3→3H2+N2) Synthesis gas (H) produced2+N2) The heat exchange temperature of the heat exchange liquid flowing out of the outlet and entering the first heat exchanger 3 is 28 ℃, and then the heat exchange liquid enters the normal temperature pressure storage tank 4 from the bottom air inlet and is stored. The synthesis gas (temperature 25 ℃, flow rate 4.182 g/s) stored in the normal temperature pressure storage tank 4 flows out from a top air outlet, enters the second heat exchanger 5 for heat exchange and temperature rise to 230 ℃, enters the third heat exchanger 6 for heat exchange and temperature rise to 510 ℃ and then enters the adiabatic reactor 8 (tubular fixed bed reactor, reaction)The length of the reactor is 1100 mm) to carry out synthetic ammonia reaction (3H)2+N2→2NH3) The reaction releases heat to raise the temperature to 730 ℃, ammonia steam flows out from an outlet and is divided into two paths, and a first pipeline 26 enters the sixth heat exchanger 10 and mixed gas (15% H) from the ninth heat exchanger 192+85%H2O) heat exchange, the mixed gas is heated to 670 ℃ and then flows into a third pipeline 28 through the mixer; the second liquid conveying pipe 25 of the other pipeline is divided into two branches, and the second pipeline 27 of one branch enters the seventh heat exchanger 11 to heat the air to 650 ℃, and then enters the high-temperature solid oxide electrolytic cell 18 to purge O2(ii) a The other branch enters a fifth heat exchanger 9 to exchange heat with the water vapor from an absorber 15, so that the temperature of the water vapor is raised to 682 ℃, the ammonia gas after heat exchange is converged with the ammonia gas of a sixth heat exchanger 10 and a seventh heat exchanger 11 to enter a second heat exchanger to exchange heat, and the ammonia gas enters a normal-temperature pressure storage tank 4 to be stored when the temperature reaches 25 ℃.
70% concentrated ammonia solution from a liquid outlet at the bottom of the absorber 15 is pressurized by a solution pump 17 to enter an eighth heat exchanger 16, part of energy is recovered and then enters the generator 12, after high-temperature steam from the fifth heat exchanger 9 exchanges heat, ammonia steam containing a small amount of steam enters a turbine 14 from a gas outlet at the top of the generator 12 to do work to generate electric power, the generated low-pressure and low-temperature ammonia steam with the pressure of 0.059MPa and the temperature of 225 ℃ enters the absorber 15 and is absorbed by 45% dilute solution from a liquid outlet at the bottom of the generator 12 in the absorber 15, and the released heat is taken away by cooling water with the temperature of 15 ℃. Cooling water enters the heat exchanger from the water inlet at the bottom of the absorber 15 for heat exchange and then is heated to 330 ℃, then enters the fifth heat exchanger 9 for heat exchange and is heated to 682 ℃, then enters the generator 12 from the water inlet at the bottom of the generator 12, water vapor after heating the ammonia water solution in the generator 12 is discharged from the water outlet at the bottom of the generator 12, the temperature is 670 ℃, the flow rate is 1.65kg/h, and the water vapor enters the high-temperature solid oxide electrolytic cell 18 along the third pipeline 28 and enters the cathode of the electrolytic cell as an electrolytic raw material.
Hydrolysis reaction takes place in the high temperature solid oxide electrolytic cell 18, the cathode portion (H)2O+2e-→H2+O2-) Obtaining the cathode product (H)2、H2O), the temperature of the mixed gas is 650 ℃, the pressure is 0.28MPa, the flow is 0.65kg/h, and the mixed gas enters a ninth heat exchanger 19 for exchangingHeating, cooling to 20 deg.C in tenth heat exchanger 20, separating water and hydrogen in separator 21, and separating H2Discharging from the top of separator 21 to obtain H2Producing a product; separated normal temperature water and a small amount of H2（15%H2+85%H2O) enters a ninth heat exchanger 19 for heat exchange and temperature rise, then enters a sixth heat exchanger 10 for temperature rise to 670 ℃, and finally enters a third pipeline 28 for circulation; o generation at the anode portion of the high temperature solid oxide electrolytic cell 182-→2e-+1/2O2The inlet material temperature is 25 ℃, the air with the flow rate of 3.88kg/h enters the seventh heat exchanger 11 to be heated to 650 ℃, and then enters the high-temperature solid oxide electrolytic cell 18 to purge the anode product (O) with the temperature of 650 ℃, the pressure of 0.28MPa and the flow rate of 4.52kg/h2），O2Firstly enters a third heat exchanger 6 for heat exchange, then enters a fourth heat exchanger 7 for cooling to the normal temperature of 20 ℃ and is discharged to obtain O2And (5) producing the product.
Example 3
The intensity of solar radiation light is 1000W/m2The light concentration ratio was 200, and the light was reflected by a heliostat field 1 to an endothermic reactor 2 (inner diameter 6.2mm, outer diameter 8.7mm, length 1220mm, reactor material made of Inconel625, nickel-based catalyst particles having a diameter of 0.4 to 0.6mm filled inside the reactor) to reach 800 ℃. Firstly, liquid ammonia with the temperature of 25 ℃ and the pressure of 30MPa flows out from a liquid outlet at the bottom of a normal-temperature pressure storage tank 4, enters a first heat exchanger 3 for heat exchange, is heated to 400 ℃, and then flows into an endothermic reactor 2 for ammonia decomposition reaction (2 NH)3→3H2+N2) Synthesis gas (H) produced2+N2) The heat exchange temperature of the heat exchange liquid flowing out of the outlet and entering the first heat exchanger 3 is 26 ℃, and then the heat exchange liquid enters the normal temperature pressure storage tank 4 from the bottom air inlet and is stored. The synthesis gas (temperature is 25 ℃, flow rate is 4.182 g/s) stored in the normal temperature pressure storage tank 4 flows out from a top gas outlet, enters the second heat exchanger 5 for heat exchange, is heated to 310 ℃, enters the third heat exchanger 6 for heat exchange, is heated to 700 ℃, enters the adiabatic reactor 8 (tubular fixed bed reactor, the reactor length is 1100 mm) to generate the synthesis ammonia reaction (3H)2+N2→2NH3) The reaction exothermed to raise the temperature to 900 deg.c and ammonia vapor fromThe outlet is divided into two paths, the first line 26 enters the sixth heat exchanger 10 and the mixed gas (15% H) from the ninth heat exchanger 192+85%H2O) heat exchange, the mixed gas is heated to 860 ℃ and then flows into a third pipeline 28; the second liquid conveying pipe 25 of the other pipeline is divided into two branches, and the second pipeline 27 of one branch enters the seventh heat exchanger 11 to heat the air to 850 ℃ and then enters the high-temperature solid oxide electrolytic cell 18 to purge O2(ii) a The other branch enters a fifth heat exchanger 9 to exchange heat with the water vapor from an absorber 15 so that the temperature of the water vapor is raised to 872 ℃, the ammonia gas after heat exchange is converged with the ammonia gas of a sixth heat exchanger 10 and a seventh heat exchanger 11 to enter a second heat exchanger 5 to exchange heat, and the ammonia gas enters a normal-temperature pressure storage tank 4 to be stored when the temperature reaches 25 ℃.
70% concentrated ammonia solution from a liquid outlet at the bottom of the absorber 15 is pressurized by a solution pump 17 to enter an eighth heat exchanger 16, part of energy is recovered and then enters the generator 12, after high-temperature steam from the fifth heat exchanger 9 exchanges heat, ammonia steam containing a small amount of steam enters a turbine 14 from a gas outlet at the top of the generator 12 to do work to generate electric power, the generated low-pressure low-temperature ammonia steam with the pressure of 0.059MPa and the temperature of 285 ℃ enters the absorber 15 and is absorbed by 45% dilute solution from a liquid outlet at the bottom of the generator 12 in the absorber 15, and the released heat is taken away by cooling water with the temperature of 15 ℃. Cooling water enters from a water inlet at the bottom of the absorber 15 for heat exchange and then is heated to 365 ℃, then enters the fifth heat exchanger 9 for heat exchange and is heated to 872 ℃, then enters the generator 12 from a water inlet at the bottom of the generator 12, water vapor after heating the ammonia water solution in the generator 12 is discharged from a water outlet at the bottom of the generator 12, the temperature is 860 ℃, the flow rate is 1.65kg/h, and the water vapor enters the high-temperature solid oxide electrolytic cell 18 along the third pipeline 28 and enters the cathode of the electrolytic cell to serve as an electrolytic raw material.
Hydrolysis reaction takes place in the high temperature solid oxide electrolytic cell 18, the cathode portion (H)2O+2e-→H2+O2-) Obtaining the cathode product (H)2、H2O), the temperature of the mixed gas is 835 ℃, the pressure is 0.28MPa, the flow is 0.63kg/H, the mixed gas firstly enters a ninth heat exchanger 19 for heat exchange, then enters a tenth heat exchanger 20 for cold extraction to the normal temperature of 30 ℃, water and hydrogen are separated in a separator 21, and the separated H2Is discharged from the top of the separator 21 to obtainH2Producing a product; separated normal temperature water and a small amount of H2（15%H2+85%H2O) enters the ninth heat exchanger 19 for heat exchange and temperature rise, then enters the sixth heat exchanger 10 for temperature rise to 860 ℃, and finally enters the third pipeline 28 for circulation; o generation at the anode portion of the high temperature solid oxide electrolytic cell 182-→2e-+1/2O2The inlet material temperature is 25 ℃, the air with the flow rate of 3.88kg/h enters the seventh heat exchanger 11 to be heated to 850 ℃, and then enters the high-temperature solid oxide electrolytic cell 18 to purge the anode product (O) with the temperature of 850 ℃, the pressure of 0.28MPa and the flow rate of 4.50kg/h2），O2Firstly enters a third heat exchanger 6 for heat exchange, then enters a fourth heat exchanger 7 for cooling to the normal temperature of 30 ℃ and is discharged to obtain O2And (5) producing the product.
Claims (4)
1. The high-temperature solid oxide water electrolysis and hydrogen production system is characterized by comprising an amino thermochemical energy storage system, a kalina circulation system and a high-temperature solid oxide water electrolysis and hydrogen production system, wherein the amino thermochemical energy system and the high-temperature solid oxide water electrolysis and hydrogen production system are in heat exchange connection through a sixth heat exchanger (10), a third heat exchanger (6) and a seventh heat exchanger (11), the amino thermochemical energy system and the kalina circulation system are in heat exchange connection through a fifth heat exchanger (9), and the kalina circulation system is connected with the high-temperature solid oxide water electrolysis and hydrogen production system to provide raw materials for the high-temperature solid oxide water electrolysis and hydrogen production system; the amino-thermal chemical energy system comprises a heliostat field (1), an endothermic reactor (2), a first heat exchanger (3), a normal-temperature pressure storage tank (4), a second heat exchanger (5), a third heat exchanger (6), an adiabatic reactor (8), a fifth heat exchanger (9) and a seventh heat exchanger (11), wherein the endothermic reactor (2), the first heat exchanger (3) and the normal-temperature pressure storage tank (4) form a circulation loop through a first gas pipe (22) and a first liquid conveying pipe (23), the second gas pipe (24) is sequentially connected with the normal-temperature pressure storage tank (4), the second heat exchanger (5), the third heat exchanger (6) and the adiabatic reactor (8), an outlet of the adiabatic reactor (8) is divided into a second liquid conveying pipe (25), a first pipeline (26) and a second pipeline (27), and the second liquid conveying pipe (25) is sequentially connected with the fifth heat exchanger (9), the second heat exchanger (5) and the normal-temperature pressure storage tank (4), a circulation loop is formed between the second air conveying pipe (24) and the second liquid conveying pipe (25), a first pipeline (26) is connected with an inlet of the sixth heat exchanger (10), an outlet of the first pipeline is connected with a pipeline between the second heat exchanger (5) and the fifth heat exchanger (9) in a converging manner, a second pipeline (27) is connected with an inlet of the seventh heat exchanger (11), an outlet of the second pipeline is connected with a pipeline between the second heat exchanger (5) and the fifth heat exchanger (9) in a converging manner, the fifth heat exchanger (9) is connected with a kalina circulation system, the kalina circulation system comprises the fifth heat exchanger (9), a generator (12), an eighth heat exchanger (16), an absorber (15), a solution pump (17) and a turbine (14), a circulation loop is formed among the generator (12), the eighth heat exchanger (16) and the absorber (15) through two pipelines, and the pipeline at the outlet at the lower end of the absorber (15) in the circulation loop is connected with the solution pump (17), an outlet of the solution pump (17) is connected with an eighth heat exchanger (16) through a pipeline, an absorber (15), a fifth heat exchanger (9) and a generator (12) are sequentially connected, an outlet at the upper end of the generator (12) is connected with a turbine (14), the turbine (14) is connected with the absorber (15), and the generator (12) is connected with a high-temperature solid oxide water electrolysis hydrogen production system; the high-temperature solid oxide water electrolysis hydrogen production system comprises a high-temperature solid oxide electrolytic cell (18), a ninth heat exchanger (19), a tenth heat exchanger (20), a separator (21), a third heat exchanger (6), a fourth heat exchanger (7), a sixth heat exchanger (10) and a seventh heat exchanger (11), wherein a cathode inlet of the high-temperature solid oxide electrolytic cell (18) is connected with a generator (12) through a third pipeline (28), a cathode outlet is connected with the ninth heat exchanger (19), the tenth heat exchanger (20) and the separator (21) are sequentially connected to form a circulation loop, an outlet of the ninth heat exchanger (19) is connected with an inlet of the sixth heat exchanger (10), an outlet of the sixth heat exchanger (10) is connected with the third pipeline (28) through a pipeline, an outlet of the seventh heat exchanger (11) is connected with an anode inlet of the high-temperature solid oxide electrolytic cell (18), the outlet is connected with a fourth heat exchanger (7) through a third heat exchanger (6).
2. The system for producing hydrogen by electrolyzing water through high-temperature solid oxide by coupling solar energy stored by amino thermochemical energy and kalina cycle according to claim 1, characterized in that a throttle valve (13) is arranged on a pipeline connecting the absorber (15) and the eighth heat exchanger (16).
3. A process for producing hydrogen by using the high-temperature solid oxide electrolyzed water hydrogen production system coupling solar amino thermochemical energy storage and kalina cycle of claim 1, comprising the steps of: the heliostat field (1) reflects sunlight to the endothermic reactor (2), an ammonia water solution in a normal temperature state flows out from an outlet at the bottom of the normal temperature pressure storage tank (4), enters the first heat exchanger (3) along a first liquid conveying pipe (23) for heat exchange and temperature rise, enters the endothermic reactor (2) along the first liquid conveying pipe (23) for ammonia decomposition reaction, generated mixed gas enters the first heat exchanger (3) along a first gas conveying pipe (22) for heat exchange, and finally flows into the endothermic reactor from an inlet at the bottom of the normal temperature pressure storage tank (4) for storage to form a circulation loop; the reaction gas flows out from the top outlet of the normal-temperature pressure storage tank (4), sequentially passes through the second heat exchanger (5) and the third heat exchanger (6) along the second gas conveying pipe (24) for heat exchange and temperature rise, then enters the adiabatic reactor (8) for ammonia synthesis reaction, ammonia generated by the reaction sequentially passes through the fifth heat exchanger (9) and the second heat exchanger (5) along the second liquid conveying pipe (25) for heat exchange, and finally enters the normal-temperature pressure storage tank (4) from the top inlet for storage to form a circulation process; an ammonia water solution circulation loop is formed between the generator (12) and the absorber (15), the strong ammonia solution from the absorber (15) is pressurized by a solution pump (17) to enter an eighth heat exchanger (16), a part of energy is recovered and then enters the generator (12), the ammonia vapor containing a small amount of water vapor enters a turbine (14) from a gas outlet at the top of the generator (12) to do work to generate electric power, the low-pressure and low-temperature ammonia vapor after power generation enters the absorber (15) to be absorbed by the dilute solution from the generator (12) and then is dischargedThe discharged heat is taken away by cooling water, and the dilute ammonia water solution of the generator (12) enters an absorber (15) after passing through an eighth heat exchanger (16) to form a circulation process; cooling water firstly enters an absorber (15) for heat absorption and temperature rise, then enters a fifth heat exchanger (9) for further heat absorption and temperature rise, finally high-temperature water vapor enters a generator (12) for heating the ammonia water solution in the generator (12), the water vapor after heating the ammonia water solution in the generator (12) is discharged from a water outlet at the bottom of the generator (12), enters a cathode of a high-temperature solid oxide electrolytic cell (18) along a third pipeline (28) as an electrolytic raw material, and a cathode product H2And H2The O enters a ninth heat exchanger (19) for heat exchange, then enters a tenth heat exchanger (20) for cold extraction to a standard state, water and hydrogen are separated in a separator (21), and separated H2Discharging from the top of the separator (21) to obtain H2The product is characterized in that the separated water firstly enters a ninth heat exchanger (19) for heat absorption and temperature rise, then enters a sixth heat exchanger (10) for further heat absorption and temperature rise, finally enters a cathode of a high-temperature solid oxide electrolytic cell (18) along a third pipeline (28) for circulation, and enters the high-temperature solid oxide electrolytic cell (18) for purging an anode product O after entering a seventh heat exchanger (11) for temperature rise2，O2Firstly enters a third heat exchanger (6) for heat exchange, then enters a fourth heat exchanger (7) for cooling to a standard state and is discharged to obtain O2And (5) producing the product.
4. The process according to claim 3, wherein the high temperature solid oxide electrolysis cell (18) is operated at a temperature in the range of 650 ℃ to 850 ℃ and the separator (21) is operated at a temperature in the range of 20 ℃ to 30 ℃.
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