Self-heating type chemical looping hydrogen production and in-situ decarbonization system and method

Abstract

The invention relates to the technical field of chemical-looping hydrogen production, and discloses a self-heating type chemical-looping hydrogen production and in-situ decarburization system and method.Hydrocarbon fuel is converted into hydrogen and carbon dioxide through a chemical-looping circular reaction, and meanwhile coupling of CO2 trapping and separation on the source side and chemical-looping hydrogen production of the hydrocarbon fuel is achieved through an absorbent; on the basis of in-situ separation of CO2, the hydrocarbon fuel conversion rate and the hydrogen yield are improved, the requirement for equipment needed by production is lowered, and meanwhile the energy efficiency level of a hydrogen production system is improved. Besides, the system can realize self-heating chemical looping hydrogen production and in-situ decarburization without external heat input through matching of a hydrogen production raw material, an oxygen carrier and CO2 absorbent particles, endothermic reduction of the oxygen carrier in the hydrogen production decarburization reactor and in-situ absorption and heat release of CO2, so that a series of problems of limited heat and mass transfer performance and the like existing in external heat driven chemical looping reaction are solved; and self-heat balance in the system can be realized, and the universality of the chemical looping technology is improved.

Description

Technical Field

[0001] The invention relates to the technical field of chemical chaining hydrogen production, and discloses a self-heating chemical chaining hydrogen production and in-situ decarbonization system and method. Background Art

[0002] Hydrogen production from hydrocarbon fuels such as natural gas occupies an important position. More than 50% of hydrogen worldwide is obtained through hydrogen production from hydrocarbon fuels such as natural gas. However, traditional methods of hydrogen production from hydrocarbon fuels, such as natural gas wet reforming hydrogen production process, will release a large amount of carbon dioxide during the hydrogen production process, and the capture of carbon dioxide will bring huge energy consumption. Therefore, it is urgent to develop methods and processes for efficient hydrogen production and low-energy decarbonization of hydrocarbon fuels. Hydrocarbon fuel chemical chain hydrogen production technology is a new and potential technology, which is expected to achieve efficient hydrogen production and low-energy CO2 separation and capture through the cyclic reaction of oxygen carriers and reactants. The existing chemical chain hydrogen production technology mainly involves a complete oxidation reaction between hydrocarbon fuels and oxygen carriers to generate water and carbon dioxide, thereby achieving source separation of CO2; the reduced oxygen carrier reacts with water vapor to generate hydrogen.

[0003] However, in order to improve the conversion rate of hydrocarbon fuels and the effect of separating CO2 from the source, the current chemical chain hydrogen production requires a high reaction temperature (the temperature of chemical chain hydrogen production for natural gas is as high as 900-1100°C). The high reaction temperature leads to a decrease in the cycle life of the oxygen carrier, harsh material selection and processing conditions for the reactor and auxiliary facilities, and a large amount of energy loss, resulting in a relatively high energy consumption for hydrogen production. Therefore, the development of chemical chain hydrogen production technology for hydrocarbon fuels at a mild reaction temperature plays an important role in improving the energy efficiency of hydrogen production and energy conservation and emission reduction benefits.

[0004] The invention patent CN110980644A published on April 10, 2020, relates to a water-based chemical chain cycle hydrogen production system and method. This method reduces oxygen carriers through the joint action of hydrocarbon fuels and water vapor, and further oxidizes the reduced oxygen carriers through water vapor to prepare H2, forming a chemical chain cycle. While reducing energy consumption, it can improve the efficiency of hydrogen production and achieve zero-energy separation of carbon dioxide in the hydrogen production process. This invention patent mainly focuses on the presence of water vapor in the two-step reaction process, one is to reduce the reduction reaction temperature, and the other is to achieve pure hydrogen production and zero-energy absorption and separation of CO2. However, this method uses medium and low temperature heat or hydrocarbon fuel combustion to power the process, and does not achieve self-heating operation of the system. At the same time, a fixed bed and a fixed structure filler solution are used, which reduces the flexibility of the system and method to adjust the ratio of oxygen carrier to absorbent.

[0005] In addition, the chemical chain process in the existing technology is mainly responsible for receiving energy to improve the quality and efficiency or outputting energy to provide energy for other processes. There are generally problems such as complex systems, the need for external heat input, and low coupling between components. At the same time, the difference in the actual functions of oxygen carriers and catalysts means that they cannot simply participate in the production process as filling materials, and there are certain obstacles to the flexible adjustment of the production process. Summary of the invention

[0006] The purpose of the present invention is to provide a self-heating chemical chain hydrogen production and in-situ decarbonization system and method, which can not only improve the conversion rate of hydrocarbon fuels and the hydrogen yield, but also improve the energy efficiency of the hydrogen production system. It can also achieve self-heating chemical chain hydrogen production and in-situ decarbonization without external heat input, avoiding a series of problems such as limited heat and mass transfer performance in external heat-driven chemical chain reactions, and can achieve self-heating balance within the system.

[0007] In order to achieve the above technical effects, the technical solution adopted by the present invention is:

[0008] A self-heating chemical chaining hydrogen production and in-situ decarbonization system, comprising:

[0009] A hydrogen production and decarbonization reactor is used to prepare hydrogen-rich gas by reacting oxidized oxygen carrier particles, CO2 absorbent particles, and hydrogen production raw materials including water vapor and hydrocarbon fuels, with a reaction temperature of 500-700°C;

[0010] The first separator is used to perform gas-solid separation on the material output from the hydrogen production and decarbonization reactor to obtain hydrogen-rich gas and a material containing a reduced oxygen carrier and CO2 absorbent particles absorbing CO2, wherein the purity of H2 in the hydrogen-rich gas is not less than 90%;

[0011] An absorbent regeneration reactor, used for desorbing CO2 from CO2 absorbent particles absorbed by CO2 in the material separated by the first separator;

[0012] The second separator is used to perform gas-solid separation on the material output from the absorbent regeneration reactor to obtain the CO2 gas produced by desorption and the material containing the reduced oxygen carrier and the regenerated CO2 absorbent particles;

[0013] The oxidation hydrogen production reactor is used to receive the particulate material separated by the second separator, and use water vapor as a hydrogen production raw material to react with the reduced oxygen carrier in the particulate material to produce hydrogen and release heat, and the heat is mainly used to maintain the autothermal operation of the autothermal chemical chain hydrogen production and in-situ decarbonization system;

[0014] The third separator is used to separate the gas-solid material output from the oxidation hydrogen production reactor to obtain hydrogen and a granular material containing regenerated CO2 absorbent particles and a preliminary oxidized oxygen carrier, wherein the purity of the hydrogen is not less than 95%;

[0015] An oxidation exothermic reactor, which is used to receive the particulate material separated by the third separator, and oxidize the oxygen carrier in the preliminary oxidation state in the particulate material with air, and release heat, wherein the heat is mainly used to maintain the autothermal operation of the autothermal chemical chain hydrogen production and in-situ decarbonization system;

[0016] The fourth separator is used to separate the gas-solid material output from the oxidation exothermic reactor to obtain oxygen-depleted air after the reaction and a material containing oxidized oxygen carriers and regenerated CO2 absorbent particles.

[0017] Furthermore, it also includes a circulation pipeline for transporting the material containing oxidized oxygen carriers and regenerated CO2 absorbent particles to the hydrogen production and decarbonization reactor, so that the oxidized oxygen carriers and regenerated CO2 absorbent particles circulate to participate in chemical chain hydrogen production and in-situ decarbonization.

[0018] Furthermore, it also includes a heat conduction component, which is used to export the heat in the oxidation hydrogen production reactor or the oxidation exothermic reactor to the absorbent regeneration reactor. The heat conduction component includes a heat pipe or a heat exchange sleeve.

[0019] Furthermore, it also includes a heat exchange system, which is used to recover the heat of the gas separated in the first separator, the second separator, the third separator or the fourth separator, and preheat the hydrocarbon fuel, the water vapor or the air input into the oxidation exothermic reactor respectively.

[0020] In order to achieve the above technical effects, the present invention also provides a method for self-heating chemical chaining hydrogen production and in-situ decarbonization, which is based on the self-heating chemical chaining hydrogen production and in-situ decarbonization system, and includes:

[0021] The hydrogen production raw materials, oxidized oxygen carrier particles, and CO2 absorbent particles are transported to a hydrogen production and decarbonization reactor to carry out a chemical reaction to prepare hydrogen-rich gas; the hydrogen production raw materials include water vapor and hydrocarbon fuels;

[0022] The first separator is used to perform gas-solid separation on the material output from the hydrogen production and decarbonization reactor to obtain hydrogen-rich gas and a CO2 absorbent particle material containing a reduced oxygen carrier and CO2 absorbed, wherein the purity of H2 in the hydrogen-rich gas is not less than 90%;

[0023] The particulate material separated by the first separator is transported to the absorbent regeneration reactor, so that the CO2 absorbent particles that absorb CO2 desorb and release CO2;

[0024] The second separator is used to separate the gas-solid material output from the absorbent regeneration reactor to obtain the desorbed CO2 gas and the material containing the reduced oxygen carrier and the regenerated CO2 absorbent particles;

[0025] The particulate material separated by the second separator is transported to an oxidation hydrogen production reactor, and water vapor is input into the oxidation hydrogen production reactor to react with the reduced oxygen carrier in the particulate material to produce hydrogen and release heat, wherein the heat is mainly used to maintain the autothermal operation of the autothermal chemical chain hydrogen production and in-situ decarbonization system;

[0026] A third separator is used to perform gas-solid separation on the material output from the oxidation hydrogen production reactor to obtain hydrogen and a particulate material containing regenerated CO2 absorbent particles and a preliminary oxidized oxygen carrier, wherein the purity of the hydrogen is not less than 95%;

[0027] The particulate material separated by the third separator is input into an oxidation exothermic reactor, and air is input into the oxidation exothermic reactor to oxidize the oxygen carrier in the preliminary oxidation state in the particulate material and release heat, wherein the heat is mainly used to maintain the autothermal operation of the autothermal chemical chain hydrogen production and in-situ decarbonization system;

[0028] The fourth separator is used to separate the gas and solid of the material output from the oxidation exothermic reactor to obtain oxygen-depleted air after the reaction and a material containing oxidized oxygen carrier and regenerated CO2 absorbent particles.

[0029] Furthermore, in the hydrogen production and decarbonization reactor, the theoretical molar ratio of the hydrocarbon fuel to the water vapor feed is in the range of 1.0 to 2.0, the mass ratio of the CO2 absorbent particles to the oxygen carrier is 0.5 to 2.0, and the active component of the oxygen carrier is 0.5 to 2.0. x H y The theoretical molar ratio range is x to 2x;

[0030] Furthermore, it also includes using a circulation pipeline to transport the material containing oxidized oxygen carriers and regenerated CO2 absorbent particles to the hydrogen production and decarbonization reactor, so that the oxidized oxygen carriers and regenerated CO2 absorbent particles circulate to participate in chemical chain hydrogen production and in-situ decarbonization.

[0031] Furthermore, a heat conducting component is used to conduct heat in the oxidation hydrogen production reactor or the oxidation exothermic reactor to the absorbent regeneration reactor, and the heat conducting component includes a heat pipe or a heat exchange sleeve.

[0032] Furthermore, a heat exchange system is used to recover the heat of the gas separated in the first separator, the second separator, the third separator or the fourth separator, and to preheat the hydrocarbon fuel, the water vapor or the air input into the oxidation exothermic reactor respectively.

[0033] Compared with the prior art, the beneficial effects of the present invention are as follows: the present invention can convert hydrocarbon fuels into hydrogen and carbon dioxide through chemical chain cycle reactions, and absorb and release CO2 through the combination and desorption process of absorbents, thereby realizing the coupling of CO2 capture and separation on the source side with hydrocarbon fuel chemical chain hydrogen production; relying on the function of in-situ separation of CO2, based on the Le Chatelier principle, the forward reaction is promoted, so that the temperature required to achieve the same reaction progress conditions is reduced, thereby improving the hydrocarbon fuel conversion rate and hydrogen production, reducing the requirements for equipment required for production, and improving the energy efficiency level of the hydrogen production system. In addition, the system can achieve self-heating chemical chain hydrogen production and in-situ decarbonization without external heat input through the matching of hydrogen production raw materials, the endothermic reduction of oxygen carriers in the hydrogen production and decarbonization reactor, and the in-situ absorption and release of heat of CO2, avoiding a series of problems such as the limited heat and mass transfer performance of external heat-driven chemical chain reactions, and can achieve self-heating balance within the system, thereby improving the versatility of chemical chain technology. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 A schematic diagram of the structure and material flow of the autothermal chemical looping hydrogen production and in-situ decarbonization system in Example 1 or 2;

[0035] Among them, 1. Hydrogen production and decarbonization reactor; 2. First separator; 3. Absorbent regeneration reactor; 4. Second separator; 5. Oxidation hydrogen production reactor; 6. Third separator; 7. Oxidation exothermic reactor; 8. Fourth separator; 9. Circulation pipeline; 10. Heat transfer component; 11. Heat exchange system. DETAILED DESCRIPTION

[0036] The present invention is further described in detail below in conjunction with the embodiments. However, it should not be understood that the scope of the above subject matter of the present invention is limited to the following embodiments, and all technologies realized based on the content of the present invention belong to the scope of the present invention.

[0037] Example

[0038] See also Figure 1 , a self-heating chemical chaining hydrogen production and in-situ decarbonization system, comprising:

[0039] The hydrogen production and decarbonization reactor 1 is used to prepare hydrogen-rich gas by reacting oxidized oxygen carrier particles, CO2 absorbent particles and hydrogen production raw materials including water vapor and hydrocarbon fuels, with a reaction temperature of 500-700°C;

[0040] The first separator 2 is used to perform gas-solid separation on the material output from the hydrogen production and decarbonization reactor 1 to obtain hydrogen-rich gas and a material containing a reduced oxygen carrier and CO2 absorbent particles absorbing CO2, wherein the purity of H2 in the hydrogen-rich gas is not less than 90%;

[0041] The absorbent regeneration reactor 3 is used to desorb CO2 from the CO2 absorbent particles absorbed by CO2 in the material separated by the first separator 2;

[0042] The second separator 4 is used to perform gas-solid separation on the material output from the absorbent regeneration reactor 3 to obtain the CO2 gas produced by desorption and the material containing the reduced oxygen carrier and the regenerated CO2 absorbent particles;

[0043] The oxidation hydrogen production reactor 5 is used to receive the particulate material separated by the second separator 4, and use water vapor as a hydrogen production raw material to react with the reduced oxygen carrier in the particulate material to produce hydrogen and release heat, and the heat is mainly used to maintain the autothermal operation of the autothermal chemical chain hydrogen production and in-situ decarbonization system;

[0044] The third separator 6 is used to separate the gas-solid material output from the oxidation hydrogen production reactor 5 to obtain hydrogen and a particulate material containing regenerated CO2 absorbent particles and a preliminary oxidized oxygen carrier, wherein the purity of the hydrogen is not less than 95%;

[0045] The oxidation exothermic reactor 7 is used to receive the particulate material separated by the third separator 6, and oxidize the oxygen carrier in the preliminary oxidation state in the particulate material with air, and release heat, and the heat is mainly used to maintain the autothermal operation of the autothermal chemical chain hydrogen production and in-situ decarbonization system;

[0046] The fourth separator 8 is used to perform gas-solid separation on the material output from the oxidation exothermic reactor 7 to obtain oxygen-depleted air after the reaction and a material containing oxidized oxygen carrier and regenerated CO2 absorbent particles.

[0047] In this embodiment, the self-heating chemical chain hydrogen production and in-situ decarbonization system can convert hydrocarbon fuels into hydrogen and carbon dioxide through chemical chain cycle reactions, and absorb and release CO2 through the combination and decomposition process of CO2 absorbent particles and CO2, thereby realizing the coupling of CO2 capture and separation on the source side with hydrocarbon fuel chemical chain hydrogen production; relying on the function of in-situ separation of CO2, based on the Le Chatelier principle, the forward reaction is promoted, so that the temperature required to achieve the same reaction progress conditions is reduced, thereby improving the hydrocarbon fuel conversion rate and hydrogen production and concentration (>90%), reducing the requirements for equipment required for production, and improving the energy efficiency level of the hydrogen production system. In addition, the system can achieve self-heating chemical chain hydrogen production and in-situ decarbonization without external heat input through the matching of hydrogen production raw materials, the endothermic reduction of oxygen carriers in the hydrogen production and decarbonization reactor 1, and the in-situ absorption and release of CO2, avoiding a series of problems such as the limited heat and mass transfer performance of external heat-driven chemical chain reactions, and can achieve self-heating balance within the system, thereby improving the versatility of chemical chain technology.

[0048] In this embodiment, the hydrogen production and decarbonization reactor, the absorbent regeneration reactor, the oxidation hydrogen production reactor, and the oxidation exothermic reactor can be moving bed reactors, or other reactor structures that can realize self-thermal chemical chain hydrogen production and in-situ decarbonization reactions.

[0049] The self-heating chemical chaining hydrogen production and in-situ decarbonization system in this embodiment also includes a circulation pipeline 9, which is used to transport the material containing the oxidized oxygen carrier and the regenerated CO2 absorbent particles to the hydrogen production and decarbonization reactor 1, so that the oxidized oxygen carrier and the regenerated CO2 absorbent particles circulate to participate in the chemical chaining hydrogen production and in-situ decarbonization. The high-temperature sensible heat carried by the inert carrier contained in the oxygen carrier and the CO2 absorbent particles that pass through the absorbent regeneration reactor 3 and the oxidation exothermic reactor 7 in sequence can be recycled, further ensuring the self-heating operation of the system.

[0050] The self-heating chemical chain hydrogen production and in-situ decarbonization system in this embodiment also includes a heat conducting component 10, which is used to export the heat in the oxidation hydrogen production reactor 5 or the oxidation exothermic reactor 7 to the absorbent regeneration reactor 3, and the heat conducting component 10 includes a heat pipe or a heat exchange sleeve. Part of the heat generated by the chemical reaction of the oxidation hydrogen production reactor 5 and the oxidation exothermic reactor 7 can be used for the heat gap required for the regeneration and heat absorption of the CO2 absorbent particles. At the same time, the heat exchange system 11 is used to recover the heat of the gas separated from the first separator 2, the second separator 4, the third separator 6 or the fourth separator 8, and the hydrocarbon fuel, the water vapor or the air input into the oxidation exothermic reactor 7 are preheated respectively, thereby completing the preheating of the gas before inputting each reactor, and reasonably matching the heat output and demand of each component of the system.

[0051] Example 2

[0052] See also Figure 1 In this embodiment, methane (CH4) is selected as hydrocarbon fuel, Ni is used as metal element M, and Li4ZrO4 is used as CO2 absorbent particles. The self-thermal chemical chaining hydrogen production and in-situ decarbonization method of the present invention is described in detail, which specifically includes the following process:

[0053] Methane, water vapor, oxygen carrier and CO2 absorbent particles enter the hydrogen production and decarbonization reactor 1 together to undergo a reduction hydrogen production reaction, and the reactor temperature range is 500-900°C. The main reaction is shown in the following formula:

[0054] Oxygen carrier reduction reaction:

[0055] The molar ratio of hydrocarbon fuel to water vapor is in the range of 1.0 to 2.0, the mass ratio of CO2 absorbent particles to oxygen carrier is in the range of 0.5 to 2.0, and the molar ratio of oxygen carrier active components to input hydrocarbon fuel is in the range of 1.0 to 2.0. The purpose of controlling the self-heating balance of the system and controlling the production is achieved by rationally configuring the molar rate ratio of hydrocarbon fuel to oxygen carrier, inert carrier and CO2 absorbent particles.

[0056] In the hydrogen production and decarbonization reactor 1 of this embodiment, the reactants are input according to the stoichiometric ratio of the chemical reaction formula listed above for comparative experiments. The experimental results show that when the reaction temperature increases from 500°C to 650°C, the reaction activity of nickel oxide and methane is enhanced, and the experimental methane conversion rate increases from 35.5% to 83.65%, while the experimental conversion rate with the addition of CO2 absorbent particles increases from 48.2% to 95.9%, and both show an overall upward trend. In addition, at the same temperature, the presence of CO2 absorbent particles accelerates the consumption of methane and increases the methane conversion rate by at least 10 percentage points. Under the condition of the same methane conversion rate, the CO2 absorbent particles reduce the temperature by about 60°C at the maximum.

[0057] It should be noted that, in addition to nickel-based oxygen carriers, other types of oxygen carriers include but are not limited to iron-based, manganese-based, copper-based, cobalt-based, tin-based, lanthanum-based metal oxides and at least one of the perovskite-type oxygen carriers are also applicable to the present invention. In order to ensure the strength of the oxygen carrier particles, an inert carrier will be added during the preparation or molding of the oxygen carrier particles, including but not limited to inert support materials such as Al2O3, YSZ, SiO2 and molecular sieves. In addition to improving the strength and life of the oxygen carrier particles, the inert carrier also has the function of a heat carrier. During actual operation, the proportion of the inert carrier in each solid particle can also be adjusted, and the sensible heat carried by the inert carrier during the particle transfer process can be used to supply part of the reaction process to assist in achieving the self-heating operation of the system. At the same time, there is a reaction system of CO2 absorbent particles and CO2 in the hydrogen production and decarbonization reactor 1 to reduce the partial pressure of CO2 in the gas phase, thereby affecting the balance of the hydrocarbon fuel and the oxygen carrier reaction, so that the balance is shifted to the right, and the conversion rate of the oxygen carrier reduction reaction can be improved under the same reaction conditions, thereby improving the conversion rate of hydrocarbon fuels and the yield and concentration of H2 (>90%). Similarly, other types of CO2 absorbent particles including but not limited to Li4SiO4, CaO, MgO, hydrotalcite-like CO2 absorbent materials are also applicable to the present invention.

[0058] After the material reacts in the hydrogen production and decarbonization reactor 1, the solid phase is transformed into CO2 absorbent particles absorbing CO2 and reduced oxygen carriers, and the gas phase component is mainly H2 (containing about 90% hydrogen).

[0059] After the outlet material of the hydrogen production and decarbonization reactor 1 is separated into gas and solid by the first separator 2, the solid enters the absorbent regeneration reactor 3, and the CO2 absorbent particles that absorb CO2 in the solid absorb heat in the regeneration reactor to undergo a decomposition reaction or desorption process, releasing the absorbed CO2. After the reaction, the solid phase is transformed into the regenerated CO2 absorbent particles and the reduced oxygen carrier, and the gas phase component is mainly CO2. In this embodiment, the heat energy required by the absorbent regeneration reactor 3 can be supplied by the oxidation hydrogen production reactor 5 and the oxidation exothermic reactor 7, and its supply method includes but is not limited to heat transfer by heat pipes, the use of heat exchange sleeves in the reactor, and other forms.

[0060] After the material at the outlet of the absorbent regeneration reactor 3 is separated from the gas and solid by the second separator 4, the solid particles all enter the oxidation hydrogen production reactor 5. The reduced oxygen carriers in the solid particles are oxidized by water vapor into high-valent oxygen carriers in the oxidation hydrogen production reactor 5, and H2 is produced at the same time. This reaction is usually an exothermic reaction. The temperature range of the hydrogen production reaction process between water vapor and reduced oxygen carriers in the oxidation hydrogen production reactor 5 is 550-800°C, and the main reaction is shown in the following formula:

[0061] Oxidative hydrogen production reaction: MO x-2 +H2O=MO x-1 +H2

[0062] After the reaction, the solid phase is transformed into regenerated CO2 absorbent particles and high-valent oxygen carriers, and the gas phase components are mainly H2 and H2O. After waste heat utilization and condensation, pure hydrogen products (or hydrogen-rich gas) can be obtained.

[0063] After the outlet material of the oxidation hydrogen production reactor 5 is separated into gas and solid by the third separator 6, the solid enters the oxidation exothermic reactor 7. The high-valent oxygen carriers in the solid and the possible unoxidized reduced oxygen carriers are further oxidized by air in the oxidation hydrogen production reactor 5. After the reaction, the solid phase is transformed into a completely oxidized form of the oxygen carrier, and the gas phase product is nitrogen that does not participate in the reaction. The complete oxidation reaction process of the high-valent oxygen carrier occurs in the oxidation exothermic reactor 7, and the reactor temperature range is 800-1000°C. The main reaction is shown in the following formula:

[0064] Exothermic oxidation reaction: 2MO x-1 +O2+4N2=2MO x +4N2

[0065] After the material at the outlet of the oxidation exothermic reactor 7 is separated from the gas and solid, the gas phase obtains nitrogen product after waste heat recovery, and the solid phase is transformed into regenerated CO2 absorbent particles and original oxygen carriers and returns to the reduction hydrogen production and decarbonization reactor 1 to react with hydrocarbon fuels again to form a chemical chain cycle.

[0066] In this embodiment, a heat exchange system 11 is composed of multiple gas phase heat exchangers to recover the heat of the gas separated in the first separator 2, the second separator 4, the third separator 6 or the fourth separator 8, and preheat the hydrocarbon fuel, the water vapor or the air input into the oxidation exothermic reactor 7 respectively. The solid particles in each reactor are evenly mixed and moved between the reactors in the form of non-fillers according to the reaction sequence. The air flow is stably introduced, and the movement of solids replaces the gas switching, so as to realize the simultaneous chemical chain multi-reaction at the same time, thereby improving the energy efficiency of the system.

[0067] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A self-heating chemical chaining hydrogen production and in-situ decarbonization system, characterized in that: include: A hydrogen production and decarbonization reactor (1) is used to produce hydrogen-rich gas by reacting oxidized oxygen carrier particles, CO2 absorbent particles and hydrogen production raw materials including water vapor and hydrocarbon fuels, with a reaction temperature of 500 to 700° C.; The first separator (2) is used to perform gas-solid separation on the material output from the hydrogen production and decarbonization reactor (1) to obtain hydrogen-rich gas and a material containing a reduced oxygen carrier and CO2 absorbent particles absorbing CO2, wherein the purity of H2 in the hydrogen-rich gas is not less than 90%; An absorbent regeneration reactor (3) is used to desorb CO2 from CO2 absorbent particles absorbed by CO2 in the material separated by the first separator (2) to remove CO2; The second separator (4) is used to perform gas-solid separation on the material output from the absorbent regeneration reactor (3) to obtain CO2 gas generated by desorption and a material containing reduced oxygen carrier and regenerated CO2 absorbent particles; The oxidation hydrogen production reactor (5) is used to receive the particulate material separated by the second separator (4), and use water vapor as a hydrogen production raw material to react with the reduced oxygen carrier in the particulate material to produce hydrogen and release heat, wherein the heat is mainly used to maintain the autothermal operation of the autothermal chemical chain hydrogen production and in-situ decarbonization system; A third separator (6) is used to perform gas-solid separation on the material output from the oxidation hydrogen production reactor (5) to obtain hydrogen and a particulate material containing regenerated CO2 absorbent particles and a preliminarily oxidized oxygen carrier, wherein the purity of the hydrogen is not less than 95%; The oxidation exothermic reactor (7) is used to receive the particulate material separated by the third separator (6), and oxidize the oxygen carrier in the initial oxidation state in the particulate material with air, and release heat, wherein the heat is mainly used to maintain the autothermal operation of the autothermal chemical chain hydrogen production and in-situ decarbonization system; The fourth separator (8) is used to separate the gas and solid of the material output from the oxidation exothermic reactor (7) to obtain oxygen-depleted air after the reaction and a material containing oxidized oxygen carrier and regenerated CO2 absorbent particles.

2. The autothermal chemical chaining hydrogen production and in-situ decarbonization system according to claim 1 is characterized in that: It also includes a circulation pipeline (9) for transporting the material containing the oxidized oxygen carrier and the regenerated CO2 absorbent particles to the hydrogen production and decarbonization reactor (1), so that the oxidized oxygen carrier and the regenerated CO2 absorbent particles circulate to participate in the chemical chain hydrogen production and in-situ decarbonization.

3. The self-thermal chemical chaining hydrogen production and in-situ decarbonization system according to claim 1 is characterized in that: It also includes a heat conducting component (10), which is used to conduct heat in the oxidation hydrogen production reactor (5) or the oxidation exothermic reactor (7) to the absorbent regeneration reactor (3), and the heat conducting component (10) includes a heat pipe or a heat exchange sleeve.

4. The self-thermal chemical chaining hydrogen production and in-situ decarbonization system according to claim 1 is characterized in that: The invention also comprises a heat exchange system (11), wherein the heat exchange system (11) is used to recover the heat of the gas separated in the first separator (2), the second separator (4), the third separator (6) or the fourth separator (8), and to preheat the hydrocarbon fuel, the water vapor or the air input into the oxidation exothermic reactor (7).

5. A method for producing hydrogen with an autothermal chemical chain and in-situ decarbonization, the method being based on the autothermal chemical chaining hydrogen production and in-situ decarbonization system according to any one of claims 1 to 4, characterized in that: include: The hydrogen production raw material, oxidized oxygen carrier particles and CO2 absorbent particles are transported to a hydrogen production and decarbonization reactor (1) to carry out a chemical reaction to produce hydrogen-rich gas; the hydrogen production raw material includes water vapor and hydrocarbon fuel; The first separator (2) is used to perform gas-solid separation on the material output from the hydrogen production and decarbonization reactor (1) to obtain hydrogen-rich gas and a CO2 absorbent particle material containing a reduced oxygen carrier and CO2 absorbed, wherein the purity of H2 in the hydrogen-rich gas is not less than 90%; The particulate material separated by the first separator (2) is transported to the absorbent regeneration reactor (3), so that the CO2 absorbent particles that absorb CO2 desorb and release CO2; The second separator (4) is used to perform gas-solid separation on the material output from the absorbent regeneration reactor (3) to obtain desorbed CO2 gas and a material containing reduced oxygen carrier and regenerated CO2 absorbent particles; The particulate material separated by the second separator (4) is transported to an oxidation hydrogen production reactor (5), and water vapor is input into the oxidation hydrogen production reactor (5) so that the water vapor reacts with the reduced oxygen carrier in the particulate material to produce hydrogen and release heat, wherein the heat is mainly used to maintain the autothermal operation of the autothermal chemical chaining hydrogen production and in-situ decarbonization system; A third separator (6) is used to separate the gas and solid of the material output from the oxidation hydrogen production reactor (5) to obtain hydrogen and a particulate material containing regenerated CO2 absorbent particles and a preliminarily oxidized oxygen carrier, wherein the purity of the hydrogen is not less than 95%; The particulate material separated by the third separator (6) is input into an oxidation exothermic reactor (7), and air is input into the oxidation exothermic reactor (7) to oxidize the oxygen carrier in the initial oxidation state in the particulate material and release heat, wherein the heat is mainly used to maintain the autothermal operation of the autothermal chemical chain hydrogen production and in-situ decarbonization system; The fourth separator (8) is used to separate the gas and solid of the material output from the oxidation exothermic reactor (7) to obtain oxygen-depleted air after the reaction and a material containing oxidized oxygen carrier and regenerated CO2 absorbent particles.

6. The method for producing hydrogen with autothermal chemical chaining and in-situ decarbonization according to claim 5, characterized in that: In the hydrogen production and decarbonization reactor (1), the theoretical molar ratio of the hydrocarbon fuel to the water vapor is in the range of 1.0 to 2.0, the mass ratio of the CO2 absorbent particles to the oxygen carrier is 0.5 to 2.0, and the active component of the oxygen carrier is in the range of 1.0 to 2.

0. x H y The theoretical molar ratio range is x~2x.

7. The method for producing hydrogen with autothermal chemical chaining and in-situ decarbonization according to claim 5, characterized in that: It also includes using a circulation pipeline (9) to transport a material containing oxidized oxygen carriers and regenerated CO2 absorbent particles to a hydrogen production and decarbonization reactor (1), so that the oxidized oxygen carriers and regenerated CO2 absorbent particles circulate to participate in chemical chain hydrogen production and in-situ decarbonization.

8. The method for producing hydrogen with autothermal chemical chaining and in-situ decarbonization according to claim 5, characterized in that: A heat conducting component (10) is used to conduct heat from an oxidation hydrogen production reactor (5) or an oxidation exothermic reactor (7) to an absorbent regeneration reactor (3), wherein the heat conducting component (10) comprises a heat pipe or a heat exchange sleeve.

9. The method for producing hydrogen with autothermal chemical chaining and in-situ decarbonization according to claim 5, characterized in that: A heat exchange system (11) is used to recover the heat of the gas separated in the first separator (2), the second separator (4), the third separator (6) or the fourth separator (8), and to preheat the hydrocarbon fuel, the water vapor or the air input into the oxidation exothermic reactor (7).

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