Integrated method and system for circulating hydrogen production and light condensation heat storage based on multifunctional catalysis-adsorbent sodium zirconate
By integrating hydrogen production and concentrated solar thermal storage using sodium zirconate as a multifunctional catalyst-adsorbent, the problems of low gasification activity and high energy consumption in biomass hydrogen production have been solved, achieving a synergistic effect of high-efficiency hydrogen production and high-efficiency thermal storage. Sodium zirconate exhibits excellent cycle stability.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- NANCHANG INST OF TECH
- Filing Date
- 2026-02-10
- Publication Date
- 2026-05-12
AI Technical Summary
Existing biomass hydrogen production technologies suffer from low gasification activity, low H2 concentration, high reactor energy consumption, low clean energy utilization, single function of catalysts/adsorbents, complex systems, high energy consumption, and poor cycle stability.
Sodium zirconate (Na2ZrO3), a multifunctional catalyst-adsorbent, is used to generate a zirconium oxide-sodium carbonate complex through a hydrogen production reaction. CO2 is separated by high-temperature reaction using concentrated solar energy, and sodium zirconate is recycled as an intermediate heat storage medium to achieve self-heating operation of the hydrogen production reaction and separation and enrichment of CO2.
It achieves improved hydrogen production efficiency and energy utilization, forms a closed-loop system, significantly enhances the synergistic effect of hydrogen production and thermal storage, and exhibits excellent cycle stability with a cycle decay rate of less than 10%.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of biochar gasification hydrogen production and thermal storage technology, specifically to an integrated method and system for cyclic hydrogen production and concentrated solar thermal storage based on the multifunctional catalyst-adsorbent sodium zirconate. Background Technology
[0002] Hydrogen energy, with its zero-carbon and high energy density advantages, has become key to the clean energy transition. However, mainstream hydrogen production technologies face bottlenecks: hydrogen production from fossil fuel reforming has high carbon emissions, and hydrogen production from water electrolysis is costly and reliant on grid peak shaving, limiting its large-scale application. Biomass resources are clean and renewable, with abundant sources and sufficient reserves (accounting for 38% of primary energy consumption in developing countries), are carbon neutral, and low in nitrogen and sulfur, making them ideal raw materials for producing "green hydrogen." my country has 6.98 billion tons of biomass energy resources annually, but nearly 600 million tons of agricultural and forestry waste are directly burned each year, wasting resources and polluting the environment. "Non-combustion utilization" of biomass for hydrogen production can solve this problem. Gasification technology is the core pathway for biomass hydrogen production, but existing technologies suffer from low gasification activity, low H2 concentration, and high reactor energy consumption.
[0003] While enhanced gasification hydrogen production integrates multiple processes, improves efficiency, and offers flexible feedstocks, with demonstration plants already built in the US, Europe, and the UK, it is hampered by CO2 capture and system energy consumption: calcium-based capture agents require low-temperature operation (<800℃), exhibit weak catalysis, struggle to produce sufficient CO2, and retain less than 30% of their initial activity after 20 cycles, resulting in high costs. Meanwhile, clean energy sources such as solar thermal energy have large reserves but low utilization rates and instability; in existing hydrogen production and thermal storage coupling technologies, conventional catalysts / adsorbents have limited functions, leading to complex systems, high energy consumption, and poor cycle stability. Therefore, developing multifunctional materials that combine catalysis, CO2 capture, and thermal storage to construct integrated systems is crucial. Sodium zirconate (Na2ZrO3) exhibits excellent cycle stability and can simultaneously achieve efficient catalysis and CO2 adsorption at the hydrogen production end and efficient thermal storage and release at the thermal storage end, potentially solving existing technical challenges and providing a new path for the coordinated development of biomass hydrogen production and clean energy storage. Summary of the Invention
[0004] The purpose of this invention is to at least solve one of the technical problems existing in the prior art, and to provide an integrated method and system for cyclic hydrogen production and concentrated solar thermal storage based on the multifunctional catalyst-adsorbent sodium zirconate.
[0005] The technical solution of the present invention is as follows: An integrated method for cyclic hydrogen production and concentrated solar thermal storage based on the multifunctional catalyst-adsorbent sodium zirconate includes the following steps: S1. Sodium zirconate, biochar and steam are introduced into a hydrogen production reactor to react and generate zirconium oxide-sodium carbonate complex. At the same time, the gas produced in the reaction is condensed to remove water and hydrogen is recovered. S2. The zirconium oxide-sodium carbonate composite obtained in step S1 is introduced into a thermal storage reactor. Under a carrier gas atmosphere, a high-temperature reaction is carried out using energy provided by concentrated solar energy. At the same time, carbon dioxide is separated and enriched and regenerated sodium zirconate is obtained through a carrier gas separation device. S3. The regenerated sodium zirconate obtained in step S2 is recycled into the hydrogen production reactor, and the reaction process of step S1 is repeated. Sodium zirconate is used as an intermediate heat storage medium to release the heat of the heat storage reactor in the hydrogen production reaction, maintain the self-heating operation of the hydrogen production reaction, and realize the recycling of sodium zirconate and continuous hydrogen production.
[0006] Preferably, in step S1, the sodium zirconate includes any one or more combinations of high-purity sodium zirconate (purity > 99%), sodium zirconate containing specific impurities, and sodium zirconate with different crystal forms.
[0007] Preferably, in step S1, the biochar is selected from one or a combination of two of bamboo charcoal and coconut shell charcoal.
[0008] Preferably, in step S1, the molar ratio of sodium zirconate to carbon in biochar is 0.25:1 to 1:1.
[0009] Preferably, in step S1, the reaction temperature of the hydrogen production reactor is controlled at 600℃~700℃.
[0010] Preferably, in step S1, the purity of the hydrogen gas is ≥85%, and there are no CH4 byproducts.
[0011] Preferably, in step S2, the temperature of the high-temperature reaction is controlled to be 750℃~1000℃.
[0012] Preferably, the carrier gas atmosphere used in steps S1 and S2 is any inert atmosphere, either a carbon dioxide-free atmosphere or a carbon dioxide-containing atmosphere.
[0013] Preferably, the sodium zirconate has cycling stability for hydrogen production and heat storage, and the cycle decay rate is less than 10% after 10 hydrogen production-heat storage cycles.
[0014] This invention also discloses a circulating hydrogen production and concentrated solar thermal storage system based on the multifunctional catalyst-adsorbent sodium zirconate, applied in the above-mentioned method, comprising: The hydrogen production reactor contains sodium zirconate and biochar; it is equipped with a pipe for introducing steam. A condensation separation device is connected to the outlet of a hydrogen production reactor to condense and remove water to obtain hydrogen. A thermal storage reactor, which is connected to a hydrogen production reactor, and is equipped with a carrier gas channel. A carrier gas separation device is connected to the outlet of a thermal storage reactor to separate and enrich CO2 gas with a concentration >99%, while simultaneously obtaining regenerated sodium zirconate.
[0015] Preferably, the thermal storage reactor is equipped with a concentrating solar energy component; the energy provided by the concentrating solar energy component is stored in sodium zirconate in the form of heat.
[0016] The beneficial effects of this invention are: in the hydrogen production stage, the invention simultaneously achieves catalytic reaction enhancement and carbon dioxide adsorption and removal, and in the heat storage stage, it stores concentrated solar energy in the form of chemical energy, forming a closed-loop system of "hydrogen production-heat storage-material regeneration", which significantly improves hydrogen production efficiency and energy utilization efficiency. Attached Figure Description
[0017] To more clearly illustrate the embodiments of the present invention, the accompanying drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0018] Figure 1 The overall flow chart of this invention is as follows: 100-hydrogen production reactor, 200-thermal storage reactor; 300-condensation separation device, 400-carrier gas separation device.
[0019] Figure 2 The graphs show the hydrogen production of comparative examples 1, 2, 3, 4, and 5 of this invention.
[0020] Figure 3 This is a comparison chart of different molar ratios in Embodiment 2 and Comparative Example 6 of the present invention.
[0021] Figure 4 These are comparison charts of different temperatures for Embodiment 3, Comparative Examples 7 and 8 of the present invention.
[0022] Figure 5 This is a comparison chart of the hydrogen production performance of different carbon sources in Comparative Examples 1 and 9 of this invention.
[0023] Figure 6 This is a graph showing the performance of sodium zirconate recycling for hydrogen production in Example 4 of the present invention.
[0024] Figure 7 This is the XRD pattern of hydrogen production using sodium zirconate in Example 5 of the present invention.
[0025] Figure 8 The graphs show the thermal storage performance of sodium zirconate in nitrogen atmosphere for Examples 6, 10, 11, and 12 of this invention.
[0026] Figure 9 The graph shows the thermal storage performance of sodium zirconate in a carbon dioxide atmosphere in Example 7 and Comparative Example 13 of the present invention.
[0027] Figure 10This is a graph showing the cyclic thermal storage performance of sodium zirconate in Example 8 of the present invention. Detailed Implementation
[0028] The technical solution of the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments. All percentages mentioned in the following embodiments are mass percentages (%). The provided chemical equations are used to further explain the reaction mechanism of the present invention, but the scope of protection of the present invention is not limited by the specific embodiments and equations.
[0029] The system of this invention includes a hydrogen production reactor 100, which contains sodium zirconate and biochar; a pipe for introducing steam is installed on it. (See reference...) Figure 1 ; A condensation separation device 300 is connected to the outlet of a hydrogen production reactor 100 to condense and remove water to obtain hydrogen. The thermal storage reactor 200 is connected to the hydrogen production reactor 100, and the thermal storage reactor is provided with a carrier gas channel. A carrier gas separator 400 is connected to the outlet of a thermal storage reactor 200 to separate carbon dioxide and obtain regenerated sodium zirconate.
[0030] Specifically, the thermal storage reactor 200 is equipped with a concentrating solar energy component, and the energy provided by the concentrating solar energy is stored in sodium zirconate in the form of heat.
[0031] The reaction that occurs in hydrogen production reactor 100: Na₂ZrO₃ + C + 2H₂O(g) = Na₂CO₃ - ZrO₂ + 2H₂(g) (Reaction 1) The reaction enthalpy change is -49 kJ / mol, which theoretically allows the hydrogen production reaction to continue operating at an autothermal temperature.
[0032] The reaction occurs in the thermal storage reactor 200: Na₂CO₃ - ZrO₂ = Na₂ZrO₃ + CO₂(g) (Reaction Equation 2)
[0033] This invention also provides a method for integrating multifunctional sodium zirconate cycle hydrogen production and concentrated solar thermal storage using the above system, the specific steps of which are as follows: S1. Na2ZrO3, biochar and water vapor are introduced into the hydrogen production reactor to generate zirconium oxide-sodium carbonate complex (ZrO2-Na2CO3) and hydrogen-rich material. Sodium zirconate includes, but is not limited to, high-purity sodium zirconate (>99%), sodium zirconate containing specific impurities, and sodium zirconate in different crystal forms.
[0034] Specifically, the biochar in step S1 includes one or a combination of two of bamboo charcoal and coconut shell charcoal.
[0035] Specifically, the molar ratio of carbon in Na2ZrO3 and biochar ranges from 0.25:1 to 1:1.
[0036] The preferred water vapor flow rate is 0.1 mL / min.
[0037] The temperature of the hydrogen production reactor is 600-700℃.
[0038] S2. The zirconium oxide-sodium carbonate composite (ZrO2-Na2CO3) obtained in step S1 is introduced into a thermal storage reactor. Energy is provided by concentrated solar energy in the atmosphere of carrier gas. At the same time, CO2 and regenerated Na2ZrO3 are obtained through a carrier gas separation device. Specifically, the temperature inside the thermal storage reactor is controlled at 750-1000℃.
[0039] Preferably, the carrier gas in steps S1 and S2 includes 99%-100% N2 and 15%-20% CO2 by volume, or it may contain no CO2.
[0040] The regenerated Na2ZrO3 obtained in steps S3 and S2 is fed back into the hydrogen production reactor to repeat steps S1 and S2 to achieve recycling; that is, by using sodium zirconate as an intermediate heat storage medium, the heat of the heat storage reactor is released in the hydrogen production reaction to maintain the self-heating operation of the hydrogen production reaction, thereby realizing the recycling of sodium zirconate and continuous hydrogen production.
[0041] The technical solution of the present invention will be further described below using the system described above with specific embodiments.
[0042] Example 1 A multifunctional sodium zirconate circulating hydrogen production and concentrated solar thermal storage system and method, the specific method of which includes the following steps: S1. Na2ZrO3, 1g of biochar, and water vapor are introduced into a hydrogen production reactor to generate a zirconium oxide-sodium carbonate complex (ZrO2-Na2CO3) and hydrogen enrichment at 600-700℃; wherein the water vapor flow rate is 0.1 mL / min. The molar ratio of carbon in Na2ZrO3 and biochar is between 0.25:1 and 1:1.
[0043] S2. Take 1g of the zirconium oxide-sodium carbonate composite (ZrO2-Na2CO3) obtained in step S1 and introduce it into the thermal storage reactor. Under the atmosphere of the carrier gas, the energy is provided by concentrated solar energy and the temperature is controlled at 750-1000℃. The reaction is carried out in the thermal storage reactor. At the same time, CO2 and regenerated Na2ZrO3 are obtained through the carrier gas separation device. The carrier gas atmosphere is 99%-100% N2 or contains 15%-20% CO2.
[0044] The regenerated Na2ZrO3 obtained in step S3 and S2 is fed back into the hydrogen production reactor to repeat steps S1 and S2 to achieve recycling.
[0045] Comparative Example 1 The preferred biochar used in this invention is 1g of bamboo charcoal. 99%-100% N2 is introduced, the reaction temperature is 650℃, the reaction time is 60 min, and the steam flow rate is 0.1 mL / min. The results in the hydrogen production reactor are as follows: Figure 2 As shown, the H2 production was 93.74 mL, and the concentration was 48.85%.
[0046] Comparative Example 2 Compared to Comparative Example 1, the only difference is that calcium oxide was added to pure bamboo charcoal, with a molar ratio of calcium oxide to carbon in the bamboo charcoal of 0.5:1. The results are as follows. Figure 2 As shown, the H2 production was 188.0 mL, and the concentration was 55.09%.
[0047] Comparative Example 3 Compared to Comparative Example 1, the only difference is that sodium carbonate was added to pure bamboo charcoal for the hydrogen production process, and the results were as follows: Figure 2 As shown, the H2 production was 402.67 mL, and the concentration was 62.35%.
[0048] Comparative Example 4 Compared with Comparative Example 1, the only difference is that calcium oxide and sodium carbonate were added to pure bamboo charcoal for the hydrogen production process, and the results were as follows: Figure 2 As shown, the H2 production was 406.75 mL, and the concentration was 67.66%.
[0049] Comparative Example 5 Compared with Comparative Example 1, the only difference is that sodium zirconate was added to pure bamboo charcoal, and the molar ratio of sodium zirconate to carbon in bamboo charcoal was 0.5:1. The results are as follows: Figure 2 As shown, the H2 production was 693.69 mL, and the concentration reached 79.57%.
[0050] Comparative Examples 1, 2, and 5 show that sodium zirconate has a stronger adsorption function than calcium oxide, and sodium zirconate can effectively catalyze reaction 1. In addition to catalyzing hydrogen production, it also adsorbs carbon dioxide, thus possessing multiple functions of catalysis and adsorption.
[0051] Example 2 Based on Comparative Example 5, the molar ratio of sodium zirconate to carbon in bamboo charcoal was changed to 0.25:1, while all other conditions remained unchanged. The results are as follows: Figure 3 As shown, the H2 production was 578.23 mL, and the concentration was 76.34%.
[0052] Comparative Example 6 Compared with Example 2, the only difference is that the molar ratio of carbon in sodium zirconate to bamboo charcoal was changed to 1:1. The result is as follows. Figure 3 As shown, the H2 production was 745.73 mL, and the concentration was 85.64%.
[0053] Examples 2 and Comparative Examples 5 and 6 demonstrate that the higher the molar ratio of carbon in sodium zirconate to biochar, the higher the H2 yield and concentration.
[0054] Example 3 The experiment was modified from Comparative Example 1, with the only difference being that the sodium zirconate catalytic gasification for hydrogen production was carried out at 600°C. The results are as follows: Figure 4 The results showed that the H2 production was 176.11 mL with a concentration of 72.34%, and no CH4 or CO gas was detected.
[0055] Comparative Example 7 Compared with Example 3, the only difference is that the temperature of the hydrogen production reaction is changed, preferably to 650°C, and the results are as follows. Figure 4 As shown, the H2 production was 693.69 mL, and the concentration was 79.57%.
[0056] Comparative Example 8 Compared to Example 3, the only difference is that the temperature of the hydrogen production reaction was changed to 700°C, and the results are as follows. Figure 4 As shown, the H2 production was 1257.12 mL, and the concentration was 75.47%.
[0057] Examples 3 and Comparative Examples 7 and 8 demonstrate that increasing the reaction temperature is beneficial for hydrogen production. The hydrogen concentration is highest at 650°C, and the hydrogen yield is highest at 700°C. Therefore, in industrial applications, a suitable temperature should be selected according to actual needs.
[0058] Comparative Example 9 Compared with Comparative Example 1, the only difference is that the type of charcoal was changed, with coconut shell charcoal being the preferred charcoal source. The results are as follows: Figure 5 As shown, the H2 production was 405.13 mL with a concentration of 76.89%.
[0059] Comparative Examples 1 and 9 demonstrate that Na2ZrO3 has broad applicability in enhancing the hydrogen production performance of biochar materials, with relatively low requirements for the charcoal material. Considering both H2 purity and yield, bamboo charcoal exhibits the best hydrogen production performance.
[0060] Example 4 Based on Comparative Example 1, sodium zirconate after hydrogen production was subjected to carbon dioxide desorption. The desorption temperature was 900℃, and the reaction time was 60 min. After desorption, the hydrogen production experiment was repeated.
[0061] like Figure 6 As shown, in the hydrogen production cycle experiment, the H2 production fluctuated, first decreasing, then increasing, then decreasing again, and then increasing again. The maximum occurred in the tenth cycle at 700.65 mL, and the minimum was in the fourth cycle at 631.42 mL, with a range of 69.23 mL. The H2 concentration showed the opposite trend, with the maximum occurring in the eighth cycle at 81.55% and the minimum in the first cycle (78.48%), with a range of 3.07%. Na2ZrO3 exhibited excellent hydrogen production cycle performance; after 10 cycles of hydrogen production testing, both the H2 production and concentration remained stable with minimal fluctuations.
[0062] Example 5 Compare the XRD patterns of Na2ZrO3 before and after hydrogen production in Comparative Example 1, as follows: Figure 7 As shown, the changes in the sample before and after the hydrogen production reaction can be observed. The results show that before hydrogen production, the diffraction peaks of Na2ZrO3 are dominant. After the hydrogen production reaction, the diffraction peaks of Na2ZrO3 basically disappear, and the XRD pattern shows that the diffraction peaks are mainly Na2CO3 and ZrO2.
[0063] Conclusion: Na2ZrO3 not only plays a catalytic role in hydrogen production, but also plays a role in CO2 adsorption. Furthermore, the adsorption process generates a ZrO2-Na2CO3 complex that catalyzes the gasification reaction.
[0064] Example 6 The preferred biochar used in this invention is 1g of bamboo charcoal. The carrier gas is a 99%-100% N2 atmosphere with a flow rate of 100mL / min. The temperature is 750℃. The results in the thermal storage reactor are as follows: Figure 8 As shown, the heat storage capacity of sodium zirconate per unit mass is 0.34 kJ / g.
[0065] Comparative Example 10 Compared with Example 7, the only difference is that the reaction temperature is changed, preferably to 800°C, and the results are as follows. Figure 8 As shown, the heat storage capacity of sodium zirconate per unit mass is 0.54 kJ / g.
[0066] Comparative Example 11 Compared with Example 7, the only difference is that the reaction temperature is changed, preferably to 850°C, and the results are as follows. Figure 8 As shown, the heat storage capacity of sodium zirconate per unit mass is 0.67 kJ / g.
[0067] Comparative Example 12 Compared with Example 7, the only difference is that the reaction temperature is changed, preferably to 900°C, and the results are as follows. Figure 8 As shown, the heat storage capacity of sodium zirconate per unit mass is 0.61 kJ / g.
[0068] Examples 6 and Comparative Examples 10, 11 and 12 show that increasing the temperature is beneficial for sodium zirconate heat storage within the temperature range of 750℃-900℃, and the heat storage effect is best at 850℃.
[0069] Example 7 The preferred biochar of this invention is 1g of bamboo charcoal, and the carrier gas is 15%-20% CO by volume. 2， The remaining gas is N2, the carrier gas flow rate is 100 mL / min, and the temperature is 900℃. The results in the thermal storage reactor are as follows: Figure 9 As shown, the heat storage capacity of sodium zirconate per unit mass is 0.20 kJ / g.
[0070] Comparative Example 13 Compared with Example 8, the only difference is that the reaction temperature was changed to 1000°C, and the result is as follows. Figure 9 As shown, the heat storage capacity of sodium zirconate per unit mass is 0.39 kJ / g.
[0071] Examples 6 and 7 demonstrate that sodium zirconate stores heat under different atmospheres.
[0072] Example 8 Based on Comparative Example 11, the desorbed sodium zirconate was subjected to carbon dioxide adsorption. The adsorption temperature was 600℃, and the reaction time was 60 min. After adsorption was completed, the heat storage experiment was repeated.
[0073] like Figure 10 As shown, in the thermal storage cycle experiment, the heat stored per unit adsorbent showed a decreasing trend, but the decrease was not significant. This indicates that Na2ZrO3 exhibits excellent thermal storage cycle performance; after 10 cycles of thermal storage testing, the heat stored per unit adsorbent remained stable with minimal fluctuations.
[0074] The above embodiments are merely preferred embodiments of the present invention, but the implementation of the present invention is not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and are included within the protection scope of the present invention.
Claims
1. An integrated method for cyclic hydrogen production and concentrated solar thermal storage based on the multifunctional catalyst-adsorbent sodium zirconate, characterized in that, Includes the following steps: S1. Sodium zirconate, biochar and steam are introduced into the hydrogen production reactor to react and generate zirconium oxide-sodium carbonate complex. This maintains the self-heating operation of the hydrogen production reactor, while the gas produced by the reaction is condensed to remove water and recover hydrogen. S2. The zirconium oxide-sodium carbonate composite obtained in step S1 is introduced into a thermal storage reactor. Under a carrier gas atmosphere, a high-temperature reaction is carried out using energy provided by concentrated solar energy. At the same time, carbon dioxide is separated and enriched and regenerated sodium zirconate is obtained through a carrier gas separation device. S3. The regenerated sodium zirconate obtained in step S2 is recycled into the hydrogen production reactor, and the reaction process of step S1 is repeated to realize the recycling of sodium zirconate and continuous hydrogen production.
2. The integrated method for cyclic hydrogen production and concentrated solar thermal storage based on the multifunctional catalyst-adsorbent sodium zirconate according to claim 1, characterized in that, In step S1, the sodium zirconate includes any one or more combinations of sodium zirconate with a purity > 99%, sodium zirconate containing specific impurities, and sodium zirconate with different crystal forms; the biochar is selected from one or a combination of two of bamboo charcoal and coconut shell charcoal.
3. The integrated method for cyclic hydrogen production and concentrated solar thermal storage based on the multifunctional catalyst-adsorbent sodium zirconate according to claim 1, characterized in that, In step S1, the molar ratio of sodium zirconate to carbon in biochar is 0.25:1 to 1:
1.
4. The integrated method for cyclic hydrogen production and concentrated solar thermal storage based on the multifunctional catalyst-adsorbent sodium zirconate according to claim 1, characterized in that, In step S1, the reaction temperature of the hydrogen production reactor is controlled at 600℃~700℃.
5. The integrated method for cyclic hydrogen production and concentrated solar thermal storage based on the multifunctional catalyst-adsorbent sodium zirconate according to claim 1, characterized in that, In step S1, the purity of the hydrogen gas is ≥85%, and there are no CH4 byproducts.
6. The integrated method for cyclic hydrogen production and concentrated solar thermal storage based on the multifunctional catalyst-adsorbent sodium zirconate according to claim 1, characterized in that, In step S2, the temperature of the high-temperature reaction is controlled at 750℃~1000℃.
7. The integrated method for cyclic hydrogen production and concentrated solar thermal storage based on the multifunctional catalyst-adsorbent sodium zirconate according to claim 1, characterized in that, The carrier gas atmosphere used in steps S1 and S2 is either a carbon dioxide-free atmosphere or a carbon dioxide-containing atmosphere, whichever is more inert.
8. The integrated method for cyclic hydrogen production and concentrated solar thermal storage based on the multifunctional catalyst-adsorbent sodium zirconate according to claim 1, characterized in that, The sodium zirconate exhibits a cycle decay rate of less than 10% after 10 hydrogen production-thermal storage cycles.
9. A circulating hydrogen production and concentrated solar thermal storage system based on the multifunctional catalyst-adsorbent sodium zirconate, applied in the method described in any one of claims 1-8, characterized in that, include: A hydrogen production reactor containing sodium zirconate and biochar; It is equipped with a pipe for introducing water vapor; A condensation separation device is connected to the outlet of a hydrogen production reactor to condense and remove water to obtain hydrogen. A thermal storage reactor, which is connected to a hydrogen production reactor, and is equipped with a carrier gas channel. A carrier gas separation device is connected to the outlet of a thermal storage reactor to separate and enrich CO2 gas with a concentration >99%, while simultaneously obtaining regenerated sodium zirconate.
10. The system according to claim 9, characterized in that, The thermal storage reactor is equipped with a concentrating solar energy component.