CN114892180B - Photovoltaic photo-thermal driven thermochemical and electrolytic coupling hydrogen production system and method - Google Patents
Photovoltaic photo-thermal driven thermochemical and electrolytic coupling hydrogen production system and method Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 232
- 239000001257 hydrogen Substances 0.000 title claims abstract description 230
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 230
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 92
- 230000008878 coupling Effects 0.000 title claims abstract description 23
- 238000010168 coupling process Methods 0.000 title claims abstract description 23
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 42
- 238000001228 spectrum Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000002918 waste heat Substances 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 122
- 229910052760 oxygen Inorganic materials 0.000 claims description 76
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 75
- 239000001301 oxygen Substances 0.000 claims description 75
- 239000000498 cooling water Substances 0.000 claims description 51
- 238000010248 power generation Methods 0.000 claims description 44
- 150000002431 hydrogen Chemical class 0.000 claims description 35
- 238000007254 oxidation reaction Methods 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 26
- 238000006722 reduction reaction Methods 0.000 claims description 17
- 238000003860 storage Methods 0.000 claims description 14
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 11
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 239000000969 carrier Substances 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
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- 229910001218 Gallium arsenide Inorganic materials 0.000 description 3
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
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- 238000005265 energy consumption Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 2
- 229910017563 LaCrO Inorganic materials 0.000 description 1
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- 239000010405 anode material Substances 0.000 description 1
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
- C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S20/00—Solar heat collectors specially adapted for particular uses or environments
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S23/00—Arrangements for concentrating solar-rays for solar heat collectors
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S40/00—Components or accessories in combination with PV modules, not provided for in groups H02S10/00 - H02S30/00
- H02S40/40—Thermal components
- H02S40/44—Means to utilise heat energy, e.g. hybrid systems producing warm water and electricity at the same time
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0272—Processes for making hydrogen or synthesis gas containing a decomposition step containing a non-catalytic decomposition step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0833—Heating by indirect heat exchange with hot fluids, other than combustion gases, product gases or non-combustive exothermic reaction product gases
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0866—Methods of heating the process for making hydrogen or synthesis gas by combination of different heating methods
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Chemical & Material Sciences (AREA)
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- Inorganic Chemistry (AREA)
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- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention provides a thermochemical and electrolytic coupling hydrogen production system driven by photovoltaic light and heat and a method thereof, wherein the system consists of a solar condenser, a sunlight frequency divider, a photovoltaic cell, a solid oxide electrolytic cell, a two-step thermochemical reactor, an adjustable heat and mass transfer unit and a regenerator; sunlight is converged and divided into short-wave-band light and long-wave-band light through a solar condenser and a sunlight frequency divider, wherein the short-wave-band light is emitted into a photovoltaic cell to generate photovoltaic power and drive high-temperature electrolysis hydrogen production, the long-wave-band light is emitted into a two-step thermochemical reactor to carry out high-temperature thermochemical water decomposition hydrogen production, a high-temperature thermochemical hydrogen production product is input into an adjustable heat and mass transfer unit to recycle substances and heat, the recycled substances and heat are input into a solid oxide electrolytic cell to serve as raw materials to carry out high-temperature electrolysis water hydrogen production, and finally waste heat of a heat regenerator is recycled to realize solar full-spectrum high-efficiency hydrogen production.
Description
Technical Field
The invention belongs to the technical field of solar energy utilization, and particularly relates to a thermochemical and electrolytic coupling hydrogen production system driven by photovoltaic light and heat and a method thereof.
Background
With the increasing demand for energy, fossil fuel consumption and carbon dioxide emissions are also rapidly increasing. Solar energy is used as clean renewable energy, the total amount of resources is huge, and the solar energy is an ideal alternative energy, but has the defects of low energy density and large irradiation fluctuation. If the solar energy is utilized to prepare hydrogen chemically, high-density and stable chemical energy can be obtained, and the advantages are obvious. In the existing method for producing hydrogen by utilizing solar energy, photovoltaic water electrolysis hydrogen production and thermochemical hydrogen production are two important hydrogen production modes.
Firstly, photovoltaic power generation is carried out by photovoltaic water electrolysis to prepare hydrogen, sunlight is directly converted into electric energy by utilizing photovoltaic effect, then the hydrogen is prepared by water electrolysis, direct current voltage is applied to two ends of a solid oxidation electrolytic cell by utilizing the electric energy produced by photovoltaic power generation, and H of a cathode of the solid oxidation electrolytic cell is prepared 2 O is decomposed to produce O 2- And H 2 Subsequently O 2- Loss of electrons through the electrolyte layer to O 2 Finally, the cathode of the solid oxidation electrolytic cell is used for producing hydrogen and anodeOxygen is extremely produced.
In the process of photovoltaic power generation, the photovoltaic cell mainly utilizes ultraviolet light and visible light with wavelengths of 200nm-800nm, solar energy of all spectrums cannot be converted into electric energy, and light which cannot realize photoelectric conversion can generate a thermal effect, so that the operating temperature of the photovoltaic cell is increased, and the photoelectric conversion efficiency of the photovoltaic cell is reduced.
In the process of hydrogen production by water electrolysis, a high-temperature electrolysis mode is adopted, so that higher energy conversion efficiency and hydrogen production rate can be obtained compared with low-temperature electrolysis. From the thermodynamic point of view, the Gibbs free energy change of the water electrolysis reaction at high temperature is reduced, the theoretical decomposition voltage of water is reduced, and the electric energy consumption is reduced. From the dynamic angle analysis, the higher operation temperature can accelerate the electrode reaction rate, so that the overpotential of the cathode and the anode is obviously reduced, the energy loss in the electrolysis process is effectively reduced, but the heat supply cost is correspondingly increased when the operation temperature of the electrolytic cell is increased.
The two-step pyrolysis hydrogen production generally utilizes the thermochemical cycle of the two-step method, utilizes the high-temperature heat energy formed by solar energy aggregation and the oxidation-reduction reaction of an oxygen carrier to decompose water, and comprises the following reaction processes:
reduction reaction:
oxidation reaction: MO (MO) X-Y +YH 2 O→MO X +YH 2
Total reaction:
the oxygen carrier is firstly reduced and oxygen is lost at a higher temperature, then oxidation reaction is carried out at a lower temperature, and the oxygen carrier for oxygen loss deprives oxygen atoms in water molecules to generate hydrogen, so that the two-step thermochemical hydrogen production is realized.
In the two-step thermochemical hydrogen production process, although the photo-thermal technology can utilize full spectrum sunlight, because the solar energy grade and the heat energy grade have larger differences, larger irreversible loss exists in the photo-thermal conversion process, high-temperature mixed gas produced by thermochemical hydrogen production still contains huge energy, and how to recycle heat is the key for improving the thermochemical hydrogen production efficiency.
Disclosure of Invention
In view of the above, the invention provides a thermochemical and electrolytic coupling hydrogen production system driven by photovoltaic light and heat and a method thereof, the system can divide sunlight into frequency for photovoltaic and photo-heat, the photovoltaic part performs photovoltaic power generation and drives high-temperature electrolytic hydrogen production, the photo-heat part performs two-step thermochemical hydrogen production, and simultaneously, substances and heat of mixed gas at the outlet of the two-step thermochemical hydrogen production are input into electrolysis Chi Jin for high-temperature electrolytic hydrogen production, so that the efficiency and speed of the high-temperature electrolytic hydrogen production are improved, and the full-spectrum high-efficiency solar hydrogen production is realized.
The technical scheme adopted for solving the technical problems is as follows:
the thermochemical and electrolytic coupling hydrogen production system driven by photovoltaic light and heat is characterized by comprising a solar concentrator, a sunlight frequency divider, a photovoltaic cell, a solid oxide electrolytic cell, a two-step thermochemical reactor, an adjustable heat and mass transfer unit and a regenerator, wherein:
the solar concentrator is used for converging sunlight and providing a high enough concentration ratio and a heat collecting temperature to meet the energy requirement of the system;
the sunlight frequency divider is used for dividing sunlight into short-wave-band light and long-wave-band light, reflecting or refracting the light into a light Fu Duan and a light hot end respectively, enabling the short-wave-band light to be injected into a photovoltaic cell at the photovoltaic end for photovoltaic power generation, and enabling the long-wave-band light to be injected into a two-step thermochemical reactor at the light hot end for two-step thermochemical hydrogen production;
The photovoltaic cell is used for photovoltaic power generation and provides electric energy for high-temperature electrolytic hydrogen production in the solid oxide electrolytic cell and operation of various parts of the system;
the two-step thermochemical reactor is used for absorbing photo-thermal energy to enable oxygen carriers in the cavity of the two-step thermochemical reactor to undergo a reduction reaction to release oxygen, and then H is sprayed into the two-step thermochemical reactor 2 O makes the oxygen carrier in the cavity produce oxidation reaction to release hydrogen, and finally collects oxidation reaction stageThe mixed gas of the high-temperature steam and the hydrogen at the outlet of the thermochemical reactor by the two-step method is introduced into an adjustable heat and mass transfer unit;
the adjustable heat and mass transfer unit is used for dividing high-temperature vapor and hydrogen gas mixture gas at the outlet of the two-step thermochemical reactor into a mass transfer flow and a heat transfer flow according to a proportion, and comprises a gas splitter, a mixer, a heat exchanger, a hydrogen separator and other parts, wherein the mass transfer flow conveys all substances and heat at the outlet of the two-step thermochemical reactor to the solid oxide electrolytic cell for high-temperature electrolytic hydrogen production, and the heat transfer flow only conveys heat at the outlet of the two-step thermochemical reactor to the solid oxide electrolytic cell for high-temperature electrolytic hydrogen production; the mixed gas of high-temperature vapor and hydrogen at the outlet of the two-step thermochemical reactor flows into a gas splitter firstly and is proportionally divided into a mass transfer flow and a heat transfer flow, and the mixed gas of the high-temperature vapor and the hydrogen of the mass transfer flow is introduced into a mixer to be mixed with newly introduced H 2 O mixing, controlling newly introduced H 2 The flow rate of O is used for adjusting the ratio of water vapor and hydrogen in the mixed gas and the temperature of the mixed gas, and then the mixed gas is introduced into a solid oxide electrolytic cell for high-temperature electrolysis hydrogen production; the high-temperature vapor and hydrogen gas mixture of the heat transfer flow stream is introduced into a heat exchanger for heat exchange, external cooling water is added into the heat exchanger to absorb the heat of the high-temperature vapor and hydrogen gas mixture and raise the temperature, the flow of the added cooling water is controlled to adjust the temperature of the cooling water, the cooling water is raised to be converted into high-temperature vapor and then introduced into a solid oxide electrolytic cell for high-temperature electrolytic hydrogen production, the high-temperature vapor and hydrogen gas mixture of the heat transfer flow stream is introduced into a hydrogen separator for separation into water and hydrogen after releasing heat for cooling, the water is reused as external cooling water of the system, and the hydrogen gas is introduced into a gas tank for storage;
the solid oxide electrolytic cell is used for carrying out high-temperature electrolysis on electric energy generated by the photovoltaic cell, high-temperature steam and mixed gas of the high-temperature steam and hydrogen which are introduced from the adjustable heat and mass transfer unit to prepare hydrogen, the solid oxide electrolytic cell generates high-temperature hydrogen at a cathode, generates high-temperature oxygen at an anode, and respectively collects the high-temperature steam and the mixed gas of the hydrogen which are not electrolyzed, the hydrogen generated by electrolysis and the oxygen generated by electrolysis, and then introduces the hydrogen into the regenerator to cool;
The heat regenerator utilizes cooling water to absorb heat of high-temperature water vapor, hydrogen gas mixture, hydrogen gas and oxygen gas which flow out of the solid oxide electrolytic cell, the hydrogen gas and the oxygen gas are respectively sent into a gas tank for storage after being cooled, the hydrogen gas mixture and the hydrogen gas mixture are cooled and then are sent into a hydrogen separator for separation into water and hydrogen gas, the water is recycled as cooling water outside the system, the hydrogen gas is sent into the gas tank for storage, and the cooling water in the heat regenerator is sent into a two-step thermochemical reactor for hydrogen production raw material in the oxidation reaction stage after absorbing the heat.
The solar energy condenser is a disc type or tower type condenser.
The sunlight frequency divider achieves the effect of photovoltaic photo-thermal coupling through the mode of concentrating light firstly and then dividing frequency or concentrating frequency firstly and then dividing frequency, when the method of concentrating light firstly and then dividing frequency is adopted, sunlight firstly enters the solar energy concentrator, the converged light is injected into the sunlight frequency divider to divide the spectrum band into short-wave light rays with 200-1200nm and long-wave light rays with residual spectrum bands, the short-wave light rays are injected into a photovoltaic cell at the photovoltaic end of the system to carry out photovoltaic power generation, and the long-wave light rays are injected into a two-step thermochemical reactor at the photo-thermal end of the system to carry out two-step thermochemical hydrogen production; when the method of dividing and concentrating the light firstly is adopted, the solar rays are firstly injected into the solar divider to divide the frequency into short-wave-band rays with the spectral wave band of 200-1200nm and long-wave-band rays with the residual spectral wave band, the short-wave-band rays are injected into the photovoltaic cells at the photovoltaic end of the system to carry out photovoltaic power generation after being concentrated by the solar concentrator, or the short-wave-band rays are directly injected into the photovoltaic cells at the photovoltaic end of the system to carry out photovoltaic power generation without being concentrated, the long-wave-band rays are injected into the solar concentrator to be concentrated, and then the two-step thermochemical reactor at the light-heat end of the system is injected to carry out two-step thermochemical hydrogen production.
The spectrum high response wave band of the photovoltaic cell is within 200-1200nm, the cooling water is arranged on the outer layer of the photovoltaic cell to absorb the waste heat of power generation to increase the power generation efficiency, the heated cooling water is introduced into the regenerator, and the heated cooling water is continuously heated into water vapor and is introduced into the two-step thermochemical reactor to serve as a hydrogen production raw material in the oxidation reaction stage.
The two-step thermochemical reactor uses iron oxide, composite iron oxide, cerium oxide or perovskite, spinel as an oxygen carrier from high temperature T H Reduced to low temperature T L Heat is released during this process, and this heat is recovered and transferred to the regenerator.
The two-step thermochemical reactor reduces the oxygen partial pressure in the oxidation stage through an inert gas purging, a mechanical pump, a thermochemical oxygen pump or a chemical sacrificial agent, and the electric energy required by the way of reducing the oxygen partial pressure is provided by photovoltaic cell power generation.
The adjustable heat and mass transfer unit utilizes the gas splitter to separate high-temperature vapor and hydrogen gas mixture at the outlet of the oxidation reaction stage of the two-step thermochemical reactor into a mass transfer flow and a heat transfer flow in proportion, the separation proportion is 0% -100%, when the gas splitter splits 100% of the high-temperature vapor and hydrogen gas mixture to be used as the mass transfer flow, all the vapor and hydrogen gas mixture discharged by the two-step thermochemical reactor is used for high-temperature electrolytic hydrogen production, when the gas splitter splits 0% of the high-temperature vapor and hydrogen gas mixture to be used as the mass transfer flow, only the heat of the vapor and hydrogen gas mixture discharged by the two-step thermochemical reactor is used for high-temperature electrolytic hydrogen production, when the mass transfer flow and the heat transfer flow are mixed and then are introduced into the solid oxide electrolytic hydrogen production, a proper amount of hydrogen in the mass transfer flow and the heat transfer flow mixture can prevent the cathode of the solid oxide electrolytic cell from being oxidized under the high-temperature high-humidity condition, the high temperature of the mass transfer flow and the heat transfer flow mixture is used for raising the electrolytic temperature of the solid oxide electrolytic cell, and the electrolytic hydrogen production is realized, and the electric quantity loss is reduced.
The gas inlet of the solid oxide electrolytic cell is the mixture of high-temperature steam and hydrogen, the gas temperature is 300-1200 ℃, the hydrogen proportion is 0% -60%, and when the hydrogen proportion is 0%, the gas inlet of the solid oxide electrolytic cell is the high-temperature steam.
The solid oxide electrolytic cell consumes four kinds of electric energy in high-temperature electrolysis, the first kind of electric energy is generated by photovoltaic power generation by receiving short-wave-band solar rays which are concentrated firstly and then subjected to frequency division by the photovoltaic cell, the second kind of electric energy is generated by photovoltaic power generation by receiving short-wave-band solar rays which are concentrated firstly and then subjected to frequency division by the photovoltaic cell, the third kind of electric energy is generated by photovoltaic power generation by receiving short-wave-band solar rays which are not concentrated after frequency division by the photovoltaic cell, and the fourth kind of electric energy is generated by photovoltaic power generation by receiving full-spectrum solar rays which are neither subjected to frequency division nor concentrated by the photovoltaic cell.
A method for producing hydrogen by thermochemical and electrolytic coupling driven by photovoltaic light and heat, comprising the following steps:
concentrating and dividing the solar rays by using a solar concentrator and a sunlight frequency divider, wherein short-wave-band rays in the solar rays are emitted into a photovoltaic end of the system, and long-wave-band rays in the solar rays are emitted into a light hot end of the system; the photovoltaic cells arranged at the photovoltaic end absorb short-wave-band light to carry out photovoltaic power generation, and provide electric energy for high-temperature electrolytic hydrogen production in the solid oxide electrolytic cell and operation of various parts of the system; the two-step thermochemical reactor arranged at the optical hot end absorbs long-wave band light, the temperature rises, the oxygen carrier undergoes a reduction reaction to release oxygen, and then H is sprayed 2 O enables oxygen carriers in the two-step thermochemical reactor to generate oxidation reaction to release hydrogen, and finally, high-temperature steam and hydrogen mixed gas in the two-step thermochemical reactor in the oxidation reaction stage is collected and introduced into an adjustable heat and mass transfer unit; the adjustable heat and mass transfer unit divides the mixed gas of high-temperature steam and hydrogen at the outlet of the two-step thermochemical reactor into a mass transfer flow and a heat transfer flow through the gas splitter, and the mixed gas of the high-temperature steam and the hydrogen of the mass transfer flow is introduced into the mixer to be mixed with newly introduced H 2 O mixing, controlling newly introduced H 2 The flow rate of O is used for adjusting the ratio of water vapor and hydrogen in the mixed gas and the temperature of the mixed gas, and then the mixed gas is introduced into a solid oxide electrolytic cell for high-temperature electrolysis hydrogen production; introducing the mixed gas of the high-temperature steam and the hydrogen of the heat transfer fluid into a heat exchanger for heat exchange, adding external cooling water into the heat exchanger to absorb the heat of the mixed gas of the high-temperature steam and the hydrogen and heating, controlling the flow of the added cooling water to adjust the temperature of the cooling water, heating the cooling water to be the high-temperature steam, and introducing solid oxide electricityThe high-temperature electrolytic hydrogen production is carried out in the decomposition tank, the heat released by the mixed gas of the high-temperature vapor and the hydrogen is cooled, then the mixed gas is introduced into the hydrogen separator to be separated into water and hydrogen, the water is recycled as cooling water outside the system, and the hydrogen is introduced into the gas tank to be stored. The solid oxide electrolytic cell takes high-temperature vapor, high-temperature vapor and hydrogen mixed gas which are introduced from the adjustable heat and mass transfer unit as raw materials, electric energy generated by the photovoltaic cell is used for high-temperature electrolytic hydrogen production, high-temperature hydrogen is generated by the cathode, high-temperature oxygen is generated by the anode, and the high-temperature vapor and hydrogen mixed gas which are not electrolyzed, hydrogen generated by electrolysis and oxygen generated by electrolysis are respectively introduced into the heat regenerator; the heat of the mixed gas of high-temperature vapor and hydrogen, the hydrogen and the oxygen which are introduced from the solid oxide electrolytic cell is absorbed by cooling water for the heat regenerator, the hydrogen and the oxygen are respectively sent to a gas tank for storage after being cooled, the mixed gas of the high-temperature vapor and the hydrogen is introduced into a hydrogen separator for separation into water and hydrogen after being cooled, the water is recycled as cooling water outside the system, the hydrogen is introduced into the gas tank for storage, and the cooling water in the heat regenerator is sent to a two-step thermochemical reactor for hydrogen production raw material in the oxidation reaction stage after absorbing the heat.
The beneficial effects of the invention are as follows:
(1) The solar energy is fully and efficiently utilized by concentrating and dividing the frequency of the solar rays, applying the short-wave-band rays to photovoltaic power generation and applying the long-wave-band rays to photo-thermal conversion and taking the energy grade difference of different spectrums of the solar energy into consideration.
(2) The heat transfer flow and the mass transfer flow can fully recover the waste heat of the two-step thermochemical hydrogen production, the operation temperature of the electrolytic cell is improved by utilizing the waste heat, the electric energy consumption in the electrolytic process is reduced, the hydrogen production rate is accelerated,
(3) The hydrogen in the mass transfer flow mixed gas is introduced into the solid oxide electrolytic cell, so that the cathode of the electrolytic cell can be protected, and the cathode is prevented from being oxidized under the conditions of high temperature and high humidity.
(4) The waste heat of the high-temperature electrolysis product and the waste heat of the photovoltaic cell power generation are recovered and are used for heating water to carry out two-step thermochemical hydrogen production again, so that the heat loss of the system is reduced, the waste heat of the photovoltaic cell power generation is absorbed, and the power generation efficiency of the photovoltaic cell is improved.
Drawings
FIG. 1 is a schematic diagram of a photovoltaic photo-thermal driven thermochemical and electrolytic coupling hydrogen production system provided by the invention;
FIG. 2 is a flow chart of a photovoltaic photo-thermal driven thermochemical and electrolytic coupling hydrogen production method provided by the invention;
FIG. 3 is an enlarged schematic view of the solar concentrator and solar divider system of FIG. 1;
FIG. 4 is a schematic diagram of another solar concentrating and frequency dividing system shown in FIG. 1;
FIG. 5 is a schematic illustration of the structure of an alternative two-step thermochemical reactor of FIG. 1;
FIG. 6 is a schematic illustration of the structure of an alternative two-step thermochemical reactor of FIG. 1;
Detailed Description
As shown in fig. 1, fig. 1 is a schematic diagram of a photovoltaic photo-thermal driven thermochemical and electrolytic coupling hydrogen production system provided by the invention, which comprises a solar concentrator a, a sunlight frequency divider b, a photovoltaic cell c, a solid oxide electrolytic cell d, a two-step thermochemical reactor e, an adjustable heat and mass transfer unit f and a regenerator g, wherein:
the solar energy condenser a is a rotary parabolic primary dish-type condenser, and a rotary motor is arranged at the bottom of the solar energy condenser a so as to track sunlight. The solar energy collector a firstly reflects solar rays to the solar energy frequency divider b, the solar energy frequency divider b then carries out secondary reflection, and the reflected rays penetrate through the light holes in the center of the collecting lens and respectively irradiate to a photovoltaic cell c at a photovoltaic end of the system and a two-step thermochemical reactor e at a light hot end of the system.
The sunlight frequency divider b is designed according to the upper half-branch type secondary mirror of the rotating hyperboloid, and is provided with a front surface and a rear surface, wherein the front surface is coated with a selective coating, so that solar rays with the wavelength of 600-1050nm can be reflected, and the rear surface is coated with a total reflection film, so that all solar rays can be reflected. The upper focus of the front surface of the sunlight frequency divider b and the upper focus of the rear surface are overlapped with the focus of the solar concentrator a, the positions of the lower focuses of the front surface and the rear surface of the sunlight frequency divider b are different, the lower focus of the front surface is positioned at a system photovoltaic end, solar rays with wavelengths of 600-1050nm can be reflected to photovoltaic cells c of the system photovoltaic ends respectively for photovoltaic power generation, the lower focus of the rear surface is positioned at a system light hot end, solar rays with wavelengths of less than or equal to 600nm and more than or equal to 1050nm can be reflected to a two-step thermochemical reactor e of the system light hot end, a photo-thermal effect heating reactor is generated, and two-step thermochemical hydrogen production is carried out.
The photovoltaic cell c adopts a light-gathering silicon cell, and the high response spectrum band of the light-gathering silicon cell is 700-1100nm and is close to the solar ray band reflected to the photovoltaic end by the front surface of the sunlight frequency divider b. The surface of the photovoltaic cell c is covered with a cooling water pipeline, the cooling water absorbs the residual heat of the photovoltaic cell c and flows into the heat regenerator g for heat recovery, the residual heat of the photovoltaic cell c is absorbed by the cooling water, the surface temperature is reduced, and the photoelectric conversion efficiency is improved. Under the wave band of 600-1050nm of solar rays, the photoelectric conversion efficiency of the photovoltaic cell c can reach 46.4%, and the photovoltaic cell c can provide power for the whole system operation (for example, power for the operation of a vacuum pump to extract oxygen in a reduction step cavity of the two-step thermochemical reactor e) and power for the high-temperature water electrolysis hydrogen production of the solid oxide electrolytic cell d.
The two-step thermochemical reactor e is used for preparing hydrogen by high-temperature thermochemical cycle decomposition of water by taking cerium oxide as an oxygen carrier, and the reaction equation is as follows:
reduction reaction:
oxidation reaction:
wherein delta red Representing oxygen vacancies, delta, of the oxygen carrier during the reduction step OX Indicating oxygen vacancies of the oxygen carrier during the oxidation step. In the hydrogen production cycle of high-temperature thermochemical cycle water decomposition, cerium oxide undergoes a reduction reaction at a higher temperature to release O 2 The oxidation reaction is carried out at a lower temperature to abstract H 2 O is generated by oxygen atoms in O 2 。
The two-step thermochemical reactor e comprises five thermochemical reaction cavities, each cavity is hemispherical, a porous cerium oxide material is placed in the cavity, a double-layer shell structure is adopted as a cavity shell, the middle of the shell is vacuumized to reduce radiation loss, and a heat preservation layer is additionally arranged between the cerium oxide material and the shell for heat insulation. The plane part of the reaction cavity is a quartz window, and solar rays reflected by the sunlight frequency divider b are emitted into the reaction cavity and spread on cerium oxide materials in the reaction cavity. The thermocouple is arranged in the reaction cavity to measure the temperature, and the external connection can be used for spraying into the air inlet pipeline of high-temperature steam, the vacuum pump for exhausting air and the exhaust pipeline.
In the two-step thermochemical cycle hydrogen production process, five cavities are heated by light and heat in turn along the circumferential rotation, the temperature in each heating cavity is heated from 900 ℃ to the reduction reaction temperature (800-1700 ℃), and then the heating is stopped. In this process, the oxygen carrier (cerium oxide) in the cavity undergoes a reduction reaction to release O 2 The vacuum pump outside the chamber is turned on to draw oxygen from the chamber to reduce the partial pressure of oxygen in the chamber. When the temperature of the cavity is reduced to the oxidation reaction temperature (800-1700 ℃), the vacuum pump is closed, the air inlet pipeline is opened, and H is sprayed into the cavity 2 O, oxidizing the oxygen carrier in the cavity to generate H 2 And generates heat, opens the exhaust duct to collect the generated gas, and the cavity will receive photo-thermal heating again and start the next cycle.
The two-step thermochemical reactor e receives photo-thermal heating in turn through five cavities to perform thermochemical circulation, and achieves the following overall effects: the two-step thermochemical reactor e can continuously receive solar heat energy, and the air inlet pipeline continuously transmits H to the two-step thermochemical reactor e 2 O, the vacuum pump is always started to extract O 2 The exhaust pipeline collects the mixed gas of high-temperature vapor and hydrogen with the temperature of 900 ℃ and the hydrogen concentration of 7.25% output by the oxidation stage of each cavity, and continuously transmits the mixed gas to the adjustable heat and mass transfer unit f.
The adjustable heat and mass transfer unit f comprises a pipe mixer delivering 100% mass transfer stream. High-temperature water vapor conveyed into adjustable heat and mass transfer unit fThe temperature of the mixed gas of the gas and the hydrogen is 900 ℃, the concentration of the hydrogen is 7.25 percent, and the mixed gas of the high-temperature vapor and the hydrogen is introduced into a pipeline mixer to be mixed with H from a regenerator g 2 O is mixed into a mixed gas of high-temperature vapor with the temperature of 700 ℃ and the hydrogen concentration of 5.4 percent, and the mixed gas is introduced into a solid oxide electrolytic cell d for high-temperature electrolysis hydrogen production.
The solid oxide electrolytic cell d is formed by ten single-piece flat plate type cathode supporting electrolytic cells through LaCrO 3 The ceramic-based composite material is formed by connecting ceramic-based materials, wherein the cathode material of the electrolytic cell is Ni/YSZ porous metal ceramic, the electrolyte is a compact YSZ layer, and the anode material is LaMnO 3 The outside of the electrolytic cell is wrapped with sealing material. The adjustable heat and mass transfer unit f transmits high-temperature vapor with the temperature of 700 ℃ and the hydrogen content of 5.4% to the cathode of the solid oxide electrolytic cell d, wherein the hydrogen can prevent the Ni-YSZ cathode from being oxidized under the conditions of high temperature and high humidity. The two ends of the solid oxide electrolytic cell d are applied with direct current voltage to carry out high-temperature water electrolysis at the operating temperature of 700 ℃ to produce hydrogen, hydrogen is produced at the cathode, and oxygen is produced at the anode. The solid oxide electrolytic cell d discharges three gases altogether, namely, the mixed gas of high-temperature steam and hydrogen which do not participate in the electrolytic reaction at the cathode end, the hydrogen generated by the electrolysis at the cathode end and the oxygen generated by the electrolysis at the anode end. The three gases are respectively conveyed into a heat regenerator g for cooling.
The regenerator g is internally provided with a high-temperature vapor and hydrogen mixed gas pipeline, a hydrogen pipeline and an oxygen pipeline which are input by the solid oxide electrolytic cell d, and a cooling water pipeline for absorbing heat. The cooling water pipeline absorbs heat of the mixed gas of the high-temperature vapor and the hydrogen, the hydrogen and the oxygen, and heats the water into the high-temperature vapor which is provided for the oxidation reaction link of the two-step thermochemical reactor e and the mass transfer flow of the adjustable heat and mass transfer unit f. The hydrogen and the oxygen are respectively sent into a gas tank for storage after being cooled, the mixed gas of the high-temperature vapor and the hydrogen is sent into a hydrogen separator for separation into water and hydrogen after being cooled, the water is sent into a water tank for recycling as system cooling water, and the hydrogen is sent into the gas tank for storage.
The embodiment is applied to the method for preparing hydrogen by thermochemical and electrolytic coupling driven by photovoltaic light and heat, which comprises the following steps: illuminating solar rays to the sunThe solar energy condenser a performs primary condensation, and condensed light irradiates the sunlight frequency divider b to perform secondary frequency division reflection. The selective coating on the front surface of the sunlight frequency divider b reflects the solar rays with the wavelength of 600-1050nm to the photovoltaic cell c at the photovoltaic end of the system for photovoltaic power generation, and the total reflection film reflects the residual solar rays with the wavelengths of less than or equal to 600nm and more than or equal to 1050nm to the two-step thermochemical reactor e at the photovoltaic end of the system to generate a photo-thermal effect, and heats the reactor for two-step thermochemical hydrogen production. The photovoltaic cell c absorbs solar rays with the wavelength of 600-1050nm to perform photovoltaic power generation, and provides electric energy for the whole system operation and the high-temperature water electrolysis hydrogen production of the solid oxide electrolytic cell d. The waste heat of the photovoltaic cell c is absorbed by surface cooling water, and the cooling water flows into the heat regenerator g for heat recovery. Each independent cavity of the two-step thermochemical reactor e firstly absorbs sunlight rays with the wavelength less than or equal to 600nm and more than or equal to 1050nm to generate a photo-thermal effect, so that the temperature in the cavity is increased from 900 ℃ to the reduction reaction temperature (800-1700 ℃), then heating is stopped, cerium oxide in the cavity is subjected to reduction reaction in the process, reduction oxygen loss is started, and O is generated 2 . Production of O from cerium oxide 2 Simultaneously, the vacuum pump is started to pump oxygen in the cavity so as to reduce the oxygen partial pressure in the cavity. When the temperature of the cavity is reduced to the oxidation reaction temperature (800-1700 ℃), the vacuum pump is closed, and the air inlet pipeline is opened to H in the cavity 2 O, at this time, cerium oxide in the cavity is oxidized to generate H 2 And heat, meanwhile, opening an exhaust pipeline to collect generated gas, wherein the gas is mixed gas of high-temperature steam with the temperature of 900 ℃ and the hydrogen concentration of 7.25%, and the mixed gas is introduced into the adjustable heat and mass transfer unit f. The adjustable heat and mass transfer unit f delivers 100% mass transfer stream. The mixed gas of high-temperature steam with the hydrogen concentration of 7.25 percent and hydrogen with the temperature of 900 ℃ is introduced into a pipeline mixer to be mixed with H from a regenerator g 2 O is mixed to be mixed into high-temperature vapor with the temperature of 700 ℃ and the hydrogen concentration of 5.4 percent, and the mixture is introduced into a solid oxide electrolytic cell d for high-temperature electrolysis hydrogen production. The solid oxide electrolytic cell d uses the mixed gas of high-temperature water vapor with the temperature of 700 ℃ and the hydrogen concentration of 5.4 percent and hydrogen as raw materials, uses the electric energy generated by a photovoltaic cell to carry out high-temperature electrolytic hydrogen production, and then uses the electric energy to carry out the high-temperature electrolytic hydrogen production in the following steps ofThe cathode produces high temperature hydrogen and high temperature oxygen at the anode. After the electrolysis of the solid oxide electrolytic cell d is completed, the mixture of the high-temperature vapor and hydrogen which are not electrolyzed, the hydrogen generated by the electrolysis and the oxygen generated by the electrolysis are respectively led into a regenerator g. The heat regenerator g absorbs heat of mixed gas of high-temperature steam and hydrogen, hydrogen and oxygen which are introduced from the solid oxide electrolytic cell by cooling water, the hydrogen and the oxygen are respectively sent into a gas tank for storage after being cooled, the mixed gas of the high-temperature steam and the hydrogen is introduced into a hydrogen separator for separation into water and hydrogen after being cooled, the water is introduced into a water tank for recycling as cooling water outside a system, the hydrogen is introduced into the gas tank for storage, the cooling water absorbs heat and is heated into high-temperature steam, and the high-temperature steam is provided for an oxidation reaction link of the two-step thermochemical reactor e as hydrogen production raw materials and an adjustable heat and mass transfer flow of the heat and mass transfer unit f for adjusting the concentration of the hydrogen in the mixed gas.
As shown in fig. 1, the photovoltaic cell c can also be a multi-junction gallium arsenide photovoltaic cell, the photovoltaic conversion efficiency of the photovoltaic cell is higher, the photovoltaic cell can bear high-temperature and high-concentration-ratio light rays, the photovoltaic cell meets the system requirements better, but the photovoltaic cell is expensive, and the system building cost can be increased.
An adjustable heat and mass transfer unit f as shown in fig. 1 may also deliver 100% of the heat and mass transfer stream, where the adjustable heat and mass transfer unit f comprises a heat exchanger. The mixed gas of the high-temperature vapor and the hydrogen which is conveyed into the adjustable heat and mass transfer unit f is introduced into a heat exchanger, cooled in the heat exchanger and then introduced into a hydrogen separator. The mixed gas is separated into water and hydrogen in a hydrogen separator, the water is introduced into a water tank to be used as cooling water of the system for recycling, and the hydrogen is introduced into the gas tank to be stored. The heat of the mixed gas is absorbed by cooling water in the heat exchanger, the temperature is raised to 700 ℃ high-temperature steam, and the high-temperature steam is introduced into the solid oxide electrolytic cell d for high-temperature electrolytic hydrogen production.
The solid oxide cell d shown in fig. 1, which performs high temperature electrolysis, consumes electrical energy in a variety of sources. The electric energy can be generated by photovoltaic power generation by receiving short-wave-band solar rays which are concentrated and then divided by the photovoltaic cell c, and the photovoltaic cell c can adopt a concentrating silicon cell or a multi-junction gallium arsenide photovoltaic cell. The electric energy can be generated by photovoltaic power generation by receiving short-wave-band solar rays which are subjected to frequency division and then condensation by the photovoltaic cell c, and the photovoltaic cell c can adopt a condensation silicon cell or a multi-junction gallium arsenide photovoltaic cell. The electric energy can also be generated by photovoltaic power generation by the photovoltaic cell c through receiving short-wave-band solar rays which are not condensed after frequency division, and the photovoltaic cell c can adopt a silicon-based photovoltaic cell. The electric energy can also be generated by the photovoltaic cell c receiving solar rays with full spectrum which are neither divided nor concentrated for photovoltaic power generation, and at the moment, the photovoltaic cell c directly receives sunlight for photovoltaic power generation, and the photovoltaic cell c can adopt a silicon-based photovoltaic cell.
Fig. 3 is an enlarged schematic view of the solar concentrator and solar divider system of fig. 1, the solar divider having front and rear surfaces, respectively front (1) and rear (2) surfaces. The solar divider b is fixed at a position where the upper focal point (a) of the front surface and the upper focal point (a) of the rear surface of the solar divider coincide with the focal point (a) of the solar condenser. The front surface (1) of the sunlight frequency divider is coated with a selective coating, can reflect the solar rays with the wavelength of 600-1050nm, and the rear surface is coated with a total reflection film (2), and can reflect all the solar rays. The lower focal points (b) of the front surface and the rear surface of the sunlight frequency divider b are different in positions, the lower focal point (b) of the front surface (1) is arranged at a system photovoltaic end, solar rays with wavelengths of 600-1050nm can be reflected to photovoltaic cells (3) at the system photovoltaic ends respectively to perform photovoltaic power generation, the lower focal point (b) of the rear surface (2) is arranged at a system photo-thermal end, solar rays with wavelengths of less than or equal to 600nm and more than or equal to 1050nm can be reflected to a two-step thermochemical reactor (4) at the system photo-thermal end, a photo-thermal effect heating reactor is generated, and two-step thermochemical hydrogen production is performed.
In one embodiment, as shown in fig. 4, a multilayer thin film filter (1) is used as the solar divider. The multi-layer film filter (1) can refract solar rays with the wavelength of 600-1050nm, and other solar rays with the wavelengths less than or equal to 600nm and more than or equal to 1050nm can penetrate the multi-layer film filter (1) without being influenced. Solar rays are condensed and then irradiated on the multilayer thin film filter (1), the solar rays with the wavelength of 600-1050nm are refracted to the photovoltaic cell (2) at the photovoltaic end of the system to carry out photovoltaic power generation, the solar rays with the wavelength of less than or equal to 600nm and more than or equal to 1050nm penetrate through the multilayer thin film filter (1), are directly irradiated on the two-step thermochemical reactor (3) at the light and heat end of the system to generate a photo-thermal effect heating reactor, and are subjected to two-step thermochemical hydrogen production.
In one embodiment, as shown in FIG. 5, an internal particle circulating fluidized bed reactor is used as a two-step thermochemical reactor with iron-based oxide, ferrite or zirconia powder as the oxygen carrier for the reaction cycle. The top of the thermochemical reactor is provided with a transparent quartz window through which solar rays are injected. The inside of the thermochemical reactor cavity is of a fluidized bed structure and is divided into an upper area and a lower area, the upper area is an annular area (1), the lower area is a draft tube (2), and a draft tube (3) is inserted between the two areas. The annular zone (1) receives direct heating of solar rays, the zone temperature is raised to 1400 ℃, and the oxygen carrier particles undergo a reduction reaction at this temperature to produce oxygen. The oxygen carrier particles then move downwards into the draft tube (2) and at the same time carry heat to the draft tube (2). The draft tube (2) is raised to 900 c, at which the oxygen carrier particles undergo oxidation reactions to produce hydrogen. Finally, the oxygen carrier particles flow into the guide pipe (3), are pushed by nitrogen at the bottom of the reactor to move upwards, flow into the annular region (1), and perform the next circulation. The high-temperature hydrogen and water vapor mixed gas in the reactor is collected by an exhaust port at the top of the reactor and is conveyed to an adjustable heat and mass transfer unit of the system for exchanging substances and heat.
In one embodiment, as shown in FIG. 6, a novel dual-chamber reactor is used as a two-step thermochemical reactor comprising two independent chambers (left chamber a and right chamber b) and a sheet light separator c with a multivalent metal oxide as the oxygen carrier. In the reaction process, the proportion of the left cavity and the right cavity which absorb the light is controlled by the sheet light separator c, the proportion of the left cavity a which absorbs the sun light is large in the initial stage, the temperature is raised to more than 1400 ℃, the proportion of the right cavity b which absorbs the sun light is small, and the temperature is raised to 900 ℃. At this time, pure nitrogen is introduced into the left cavity a to wash the reaction cavity, the oxygen carrier in the left cavity a performs a reduction reaction to generate oxygen, water vapor is introduced into the right cavity b, and the oxygen carrier in the right cavity b performs an oxidation reaction to generate hydrogen. After the oxygen carriers in the two cavities react fully, the proportion of light distributed by the sheet light separator c is regulated, the proportion of solar rays absorbed by the left cavity a is reduced, the temperature is reduced to 900 ℃, the proportion of solar rays absorbed by the right cavity b is increased, and the temperature is raised to more than 1400 ℃. At this time, water vapor is introduced into the left cavity a, the oxygen carrier in the left cavity a performs oxidation reaction to generate hydrogen, pure nitrogen is introduced into the right cavity b to wash the reaction cavity, and the oxygen carrier in the right cavity b performs reduction reaction to generate oxygen. Finally, the two reaction cavities are circularly subjected to two-step thermochemical reaction, high-temperature hydrogen and steam mixed gas in the two cavities are collected at an exhaust port of the reactor, and the mixed gas is conveyed to an adjustable heat and mass transfer unit of the system for exchanging substances and heat.
Accordingly, the description of the specific embodiments of the present invention is not intended to limit the spirit and scope of the invention, and any modifications and improvements made by those skilled in the art will still fall within the scope of the invention without departing from the technical scope of the invention.
Claims (10)
1. The thermochemical and electrolytic coupling hydrogen production system driven by photovoltaic light and heat is characterized by comprising a solar concentrator (1), a sunlight frequency divider (2), a photovoltaic cell (3), a solid oxide electrolytic cell (4), a two-step thermochemical reactor (5), an adjustable heat and mass transfer unit (6) and a regenerator (7), wherein:
the solar concentrator (1) is used for converging sunlight and providing a high enough concentration ratio and a heat collection temperature to meet the energy requirement of the system;
the sunlight frequency divider (2) is used for dividing sunlight into short-wave-band light and long-wave-band light, reflecting or refracting the light Fu Duan and the light-heat end respectively, injecting the short-wave-band light into the photovoltaic cell (3) at the photovoltaic end for photovoltaic power generation, and injecting the long-wave-band light into the two-step thermochemical reactor (5) at the light-heat end for two-step thermochemical hydrogen production;
the photovoltaic cell (3) is used for photovoltaic power generation and provides electric energy for high-temperature electrolytic hydrogen production in the solid oxide electrolytic cell (4) and operation of all parts of the system;
A two-step thermochemical reactor (5) for absorbing photo-thermal energyThe amount of the catalyst enables oxygen carriers in the cavity of the two-step thermochemical reactor (5) to undergo a reduction reaction to release oxygen, and then H is sprayed into the two-step thermochemical reactor (5) 2 O enables oxygen carriers in the cavity to generate oxidation reaction to release hydrogen, finally, mixed gas of high-temperature steam and hydrogen at the outlet of a two-step thermochemical reactor (5) in the oxidation reaction stage is collected, and the mixed gas of the high-temperature steam and the hydrogen is introduced into an adjustable heat and mass transfer unit (6);
an adjustable heat and mass transfer unit (6) for dividing the mixed gas of the high-temperature steam and the hydrogen gas at the outlet of the two-step thermochemical reactor (5) into a mass transfer flow (a) and a heat transfer flow (b) according to a proportion, wherein the mass transfer flow (a) comprises a gas splitter (c), a mixer (d), a heat exchanger (e) and a hydrogen separator (f), the mass transfer flow (a) is used for conveying all substances and heat at the outlet of the two-step thermochemical reactor (5) to the solid oxide electrolytic cell (4) for high-temperature electrolytic hydrogen production, and the heat transfer flow (b) is used for conveying only the heat of the product at the outlet of the two-step thermochemical reactor (5) to the solid oxide electrolytic cell (4) for high-temperature electrolytic hydrogen production; the mixed gas of high-temperature steam and hydrogen at the outlet of the two-step thermochemical reactor (5) flows into a gas splitter (c) at first and is divided into a mass transfer flow (a) and a heat transfer flow (b) according to a proportion, and the mixed gas of the high-temperature steam and the hydrogen of the mass transfer flow (a) is introduced into a mixer (d) to be mixed with the newly introduced H 2 O mixing, controlling newly introduced H 2 The flow rate of O is used for adjusting the ratio of water vapor and hydrogen in the mixed gas and the temperature of the mixed gas, and then the mixed gas is introduced into a solid oxide electrolytic cell (4) for high-temperature electrolysis to prepare hydrogen; the high-temperature steam and hydrogen gas mixture of the heat transfer flow (b) is led into a heat exchanger (e) for heat exchange, external cooling water is added into the heat exchanger (e) to absorb the heat of the high-temperature steam and hydrogen gas mixture and raise the temperature, the flow of the cooling water is controlled to adjust the temperature of the cooling water, the cooling water is heated to be converted into high-temperature steam and then is led into a solid oxide electrolytic cell (4) for high-temperature electrolytic hydrogen production, the high-temperature steam and hydrogen gas mixture of the heat transfer flow (b) is led into a hydrogen separator (f) for separation into water and hydrogen gas after releasing heat for cooling, the water is recycled as external cooling water of the system, and the hydrogen gas is led into a gas tank for storage;
the solid oxide electrolytic cell (4) is used for carrying out high-temperature electrolysis on electric energy generated by the photovoltaic cell (3) and high-temperature steam, high-temperature steam and hydrogen mixed gas which are introduced from the adjustable heat and mass transfer unit (6) to prepare hydrogen, the solid oxide electrolytic cell (4) generates high-temperature hydrogen at a cathode, generates high-temperature oxygen at an anode, and respectively collects the high-temperature steam and hydrogen mixed gas which are not electrolyzed, hydrogen generated by electrolysis and oxygen generated by electrolysis, and then introduces the hydrogen into the regenerator (7) to cool;
The regenerator (7) utilizes cooling water to absorb heat of high-temperature vapor, hydrogen gas mixture, hydrogen gas and oxygen gas flowing out of the solid oxide electrolytic cell (4), the hydrogen gas and the oxygen gas are respectively sent into a gas tank for storage after being cooled, the high-temperature vapor and the hydrogen gas mixture are led into a hydrogen separator (f) for separation into water and hydrogen gas after being cooled, the water is recycled as cooling water outside the system, the hydrogen gas is led into the gas tank for storage, and the cooling water in the regenerator (7) absorbs heat and is sent into the two-step thermochemical reactor (5) for hydrogen production raw materials in the oxidation reaction stage.
2. A photovoltaic photo-thermally driven thermochemical and electrolytic coupling hydrogen production system according to claim 1, characterized in that the solar concentrator (1) is a dish-type or tower-type concentrator.
3. The thermochemical and electrolytic coupling hydrogen production system driven by photovoltaic light and heat according to claim 1 is characterized in that the sunlight frequency divider (2) achieves the effect of photovoltaic light and heat coupling in a mode of concentrating light firstly and then dividing frequency or concentrating frequency firstly and then concentrating frequency, when the method of concentrating light firstly and then dividing frequency is adopted, sunlight firstly enters the solar concentrator (1), the concentrated sunlight enters the sunlight frequency divider (2) to divide the concentrated sunlight into short-wave light with a spectrum wave band of 200-1200nm and long-wave light with a residual spectrum wave band, the short-wave light enters the photovoltaic cell (3) at the photovoltaic end of the system to carry out photovoltaic power generation, and the long-wave light enters the two-step thermochemical reactor (5) at the photo-thermal end of the system to carry out two-step thermochemical hydrogen production; when the method of dividing frequency and concentrating light is adopted, solar rays are firstly injected into a solar light frequency divider (2) to divide frequency into short-wave-band rays with the spectral wave band of 200-1200nm and long-wave-band rays with the residual spectral wave band, the short-wave-band rays are injected into a photovoltaic cell (3) at the photovoltaic end of the system to carry out photovoltaic power generation after being concentrated by a solar concentrator (1), or the short-wave-band rays are directly injected into the photovoltaic cell (3) at the photovoltaic end of the system without being concentrated to carry out photovoltaic power generation, the long-wave-band rays are injected into the solar concentrator (1) to concentrate light, and then are injected into a two-step thermochemical reactor (5) at the photo-thermal end of the system to carry out two-step thermochemical hydrogen production.
4. The photovoltaic photo-thermal driven thermochemical and electrolytic coupling hydrogen production system according to claim 1, wherein the spectrum high response wave band of the photovoltaic cell (3) is within 200-1200nm, the cooling water is arranged on the outer layer of the photovoltaic cell (3) to absorb the waste heat of power generation to increase the power generation efficiency, the heated cooling water is introduced into the regenerator (7), and the heated cooling water is continuously heated to steam and is introduced into the two-step thermochemical reactor (5) to serve as hydrogen production raw materials in the oxidation reaction stage.
5. The photovoltaic photo-thermally driven thermochemical and electrolytic coupling hydrogen production system according to claim 1, wherein the two-step thermochemical reactor (5) uses iron oxide, composite iron oxide, cerium oxide or perovskite, spinel as oxygen carrier, oxygen carrier from high temperature T H Reduced to low temperature T L Heat is released, and this heat is recovered and transferred to the regenerator (7).
6. The photovoltaic photo-thermally driven thermochemical and electrolytic coupling hydrogen production system of claim 1, wherein the two-step thermochemical reactor (5) reduces the partial pressure of oxygen during the oxidation stage by means of inert gas purging, mechanical pumps, thermochemical oxygen pumps or chemical sacrificial agents, and the electrical energy required to reduce the partial pressure of oxygen is provided by the photovoltaic cell (3) power generation.
7. The photovoltaic photo-thermal driven thermochemical and electrolytic coupling hydrogen production system according to claim 1, wherein the adjustable heat and mass transfer unit (6) separates the mixed gas of high-temperature vapor and hydrogen gas at the outlet of the oxidation reaction stage of the two-step thermochemical reactor (5) into a mass transfer stream (a) and a heat transfer stream (b) by using the gas splitter (c), the separation ratio is 0% -100%, when the gas splitter (c) splits 100% of the mixed gas of high-temperature vapor and hydrogen gas as the mass transfer stream (a), all the mixed gas of water vapor and hydrogen gas discharged from the two-step thermochemical reactor (5) is used for high-temperature electrolytic hydrogen production, when the mixed gas of high-temperature vapor and hydrogen gas at the outlet of the gas splitter (c) is split into the mixed gas of high-temperature vapor and hydrogen gas as the mass transfer stream (a), the mixed gas of high-temperature electrolytic hydrogen gas and the mixed gas discharged from the two-step thermochemical reactor (5) is used for high-temperature electrolytic hydrogen production, when the mixed gas of the mixed gas (a) and the heat transfer stream (b) is fed into the solid oxide electrolytic cell (4) to perform electrolysis, the mixed gas of high-temperature stream (b) is oxidized at a proper amount under the high-temperature conditions, and the mixed gas of the high-temperature electrolytic stream (4) is prevented from oxidizing the solid electrolytic stream (b) with the high-temperature stream (b) at the high temperature of the high temperature electrolytic cell (4), so as to reduce the electric quantity loss in the electrolysis process.
8. The photovoltaic photo-thermal driven thermochemical and electrolytic coupling hydrogen production system according to claim 1, wherein the gas inlet of the solid oxide electrolytic cell (4) is a mixed gas of high-temperature steam and hydrogen, the gas temperature is 300-1200 ℃, the hydrogen ratio is 0% -60%, and when the hydrogen ratio is 0%, the gas inlet of the solid oxide electrolytic cell (4) is high-temperature steam.
9. The thermochemical and electrolytic coupling hydrogen production system driven by photovoltaic light and heat according to claim 1 is characterized in that the electric energy consumed by high-temperature electrolysis of the solid oxide electrolytic cell (4) has four sources, the first electric energy is generated by photovoltaic power generation by receiving short-wave solar rays which are concentrated first and then divided, the second electric energy is generated by photovoltaic power generation by receiving short-wave solar rays which are concentrated first and then divided by the photovoltaic cell (3), the third electric energy is generated by photovoltaic power generation by receiving short-wave solar rays which are not concentrated after being divided by the photovoltaic cell (3), and the fourth electric energy is generated by photovoltaic power generation by receiving full-spectrum solar rays which are neither divided nor concentrated by the photovoltaic cell (3).
10. A method of producing hydrogen by thermochemical and electrolytic coupling driven by photovoltaic light and heat, applied to the system as claimed in any one of claims 1 to 9, characterized in that it comprises:
concentrating and dividing the solar rays by using a solar concentrator (1) and a sunlight frequency divider (2), wherein short-wave-band rays in the solar rays are emitted into a photovoltaic end of the system, and long-wave-band rays in the solar rays are emitted into a light end of the system;
a photovoltaic cell (3) arranged at the photovoltaic end absorbs short-wave light to carry out photovoltaic power generation, and provides electric energy for high-temperature electrolytic hydrogen production in a solid oxide electrolytic cell (4) and operation of various parts of the system;
the two-step thermochemical reactor (5) arranged at the light and hot end absorbs the light with long wave band and the temperature rises to lead the oxygen carrier to undergo reduction reaction to release oxygen, and then the oxygen carrier is sprayed into H 2 O enables oxygen carriers in the two-step thermochemical reactor (5) to generate oxidation reaction to release hydrogen, and finally, high-temperature steam and hydrogen mixed gas in the two-step thermochemical reactor (5) in the oxidation reaction stage are collected and introduced into an adjustable heat and mass transfer unit (6);
an adjustable heat and mass transfer unit (6) for dividing the mixture of high-temperature steam and hydrogen at the outlet of the two-step thermochemical reactor (5) into a mass transfer flow (a) and a heat transfer flow (b) through a gas splitter (c), and introducing the mixture of high-temperature steam and hydrogen at the mass transfer flow (a) into a mixer (d) to be mixed with newly introduced H 2 O mixing, controlling newly introduced H 2 The flow rate of O is used for adjusting the ratio of water vapor and hydrogen in the mixed gas and the temperature of the mixed gas, and then the mixed gas is introduced into a solid oxide electrolytic cell (4) for high-temperature electrolysis to prepare hydrogen; the high-temperature steam and hydrogen gas mixture of the heat transfer fluid (b) is introduced into a heat exchanger (e) for heat exchange, external cooling water is added into the heat exchanger (e) to absorb the heat of the high-temperature steam and hydrogen gas mixture and raise the temperature, the flow of the added cooling water is controlled to adjust the temperature of the cooling water, and the cooling water is introduced into solid oxide after being heated to high-temperature steamThe electrolytic cell (4) carries out high-temperature electrolysis to prepare hydrogen, and the mixed gas of the high-temperature vapor and the hydrogen emits heat to be cooled, and then the cooled mixed gas is introduced into the hydrogen separator (f) to be separated into water and hydrogen, the water is recycled as cooling water outside the system, and the hydrogen is introduced into the gas tank to be stored;
the solid oxide electrolytic cell (4) takes high-temperature steam, high-temperature steam and hydrogen mixed gas which are introduced from the adjustable heat and mass transfer unit (6) as raw materials, electric energy generated by the photovoltaic cell (3) is used for high-temperature electrolytic hydrogen production, high-temperature hydrogen is produced by the cathode, high-temperature oxygen is produced by the anode, and the high-temperature steam and hydrogen mixed gas which are not electrolyzed, hydrogen generated by electrolysis and oxygen generated by electrolysis are respectively introduced into the regenerator (7);
The heat regenerator (7) absorbs heat of mixed gas of high-temperature vapor and hydrogen, hydrogen and oxygen which are introduced from the solid oxide electrolytic cell (4) through cooling water, the hydrogen and the oxygen are respectively sent into a gas tank for storage after being cooled, the mixed gas of the high-temperature vapor and the hydrogen is introduced into the hydrogen separator (f) for separation into water and hydrogen after being cooled, the water is recycled as cooling water outside the system, the hydrogen is introduced into the gas tank for storage, and the cooling water in the heat regenerator (7) is sent into the two-step thermochemical reactor (5) for hydrogen production raw materials after absorbing the heat.
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