Chemical looping reaction hydrogen production system and method

Abstract

The application provides a chemical chain reaction hydrogen production system and method. The system comprises a hydrocarbon conversion syngas reactor, a first hydrogen production reactor, a first gas-solid separation device, a syngas oxidation reactor, a second gas-solid separation device, a second hydrogen production reactor and a third gas-solid separation device; a solid phase product outlet of the hydrocarbon conversion syngas reactor is connected with a solid feed inlet of the first hydrogen production reactor, a product outlet of the first hydrogen production reactor is connected with a feed inlet of the first gas-solid separation device, a gas phase product outlet of the hydrocarbon conversion syngas reactor is connected with a gas feed inlet of the syngas oxidation reactor, a product outlet of the syngas oxidation reactor is connected with a feed inlet of the second gas-solid separation device, a solid phase product outlet of the second gas-solid separation device is connected with a solid feed inlet of the second hydrogen production reactor, and a product outlet of the second hydrogen production reactor is connected with a feed inlet of the third gas-solid separation device.

Description

Technical Field

[0001] This invention relates to a chemical chain reaction hydrogen production system and method. Background Technology

[0002] Currently, hydrogen production processes based on methane steam reforming dominate the market. Using syngas as an intermediate product, the gas is cooled and then converted to hydrogen-rich form via a water-gas shift reaction. Finally, CO2 is separated and H2 is purified through physical or chemical absorption methods. Because steam reforming is a strongly endothermic reaction, industrially, tubular reactors are typically used. Nickel-based catalysts are loaded onto the inner walls of the tubes to activate hydrocarbons, while heat is provided outside the tubes through fuel and air combustion. This places high demands on the reactor structure and materials. Furthermore, the CO2 produced during combustion mixes with residual air, requiring additional separation processes for carbon capture. Another way to provide the heat needed for steam reforming is to introduce pure oxygen into the reaction system for direct heating, but this requires expensive air separation equipment. Traditional thermochemical hydrogen production processes perform hydrocarbon separation at the end of the process, resulting in low integration of energy conversion and product separation, leading to numerous unit operations and high energy consumption for gas separation.

[0003] To overcome the above problems, improve energy conversion efficiency, and reduce production costs, researchers are constantly developing new thermochemical hydrogen production processes. Among them, chemical looping, as an advanced and efficient fuel conversion technology, can achieve near-zero energy consumption in-situ separation of products while producing hydrogen, and has received widespread attention.

[0004] Currently, chemical chain hydrogen production is mainly conducted in laboratory research and has not yet been scaled up for industrial production. Researchers have systematically developed oxygen carriers and processes. The main goals of oxygen carrier development are: (1) to improve the activity and selectivity of methane conversion, so that the C in methane is ultimately released and captured as CO2, thereby improving the carbon capture rate; (2) to optimize the oxygen carrier formulation or control the reaction time to inhibit carbon deposition in the reaction, thereby improving the hydrogen purity of the steam reforming unit; (3) to add additives or optimize the composition and structure of the oxygen carrier to reduce the methane conversion temperature, improve the oxygen utilization rate of the oxygen carrier, reduce the number of oxygen carrier cycles, and reduce the reaction energy consumption. The main objectives of the process system development are: (1) design of the reaction process flow, taking into account the heat absorption and release effects between different reactions, and improving the energy utilization efficiency of the reaction; (2) selection of reactor form, with fluidized bed and moving bed as the mainstream, to realize the efficient circulation of oxygen carrier in different reaction processes, realize the oxygen absorption and release process, and improve the compatibility effect of carbon capture and hydrogen production process; (3) reactor structure design, to improve the gas-solid mass transfer and heat transfer efficiency, and improve the reaction conversion rate.

[0005] CN115650168A discloses a methane chemical loop hydrogen production technology, employing a dual fixed-bed reactor and using an iron-nickel-alumina composite oxygen carrier to achieve methane combustion and pure water hydrogen production. This technology has the following main drawbacks: The dual fixed-bed reactor configuration for methane combustion and water hydrogen production results in an intermittent operation, requiring continuous monitoring and switching of the gas collection device. Furthermore, to eliminate carbon buildup, a carbon deposit gasification device is added, increasing methane consumption.

[0006] CN113753857A discloses a methane chemical loop hydrogen production technology, which combines a methane reforming reactor, a hydrogen production reactor, and a controller to realize the dry reforming reaction of methane and the process of producing hydrogen from water. The main drawbacks of this technology are as follows: It first performs a reforming process of methane and carbon dioxide gas, then uses the reformed syngas through a chemical loop process to achieve complete conversion of the syngas and the production of pure hydrogen from water vapor. The technology relies on a controller to close valves to control the entry of reformed gas into different reactors and the production of pure hydrogen from water vapor. This results in a complex device structure, which is not conducive to long-term continuous reaction operation.

[0007] CN107539949A discloses a chemical loop hydrogen production technology for methane. This technology employs a four-bed countercurrent moving bed reactor. In the methane combustion stage, a dual-bed countercurrent configuration is used to achieve further combustion of methane. Subsequently, hydrogen production from water and oxidation of the oxygen carrier are achieved through a water-to-hydrogen fluidized bed and an air riser reactor. The main drawback of this technology is that while the device achieves both methane combustion and water-to-hydrogen processes, there is a mismatch between the complete combustion of methane and the water-to-hydrogen process, resulting in low hydrogen yield and purity in the water-to-hydrogen stage.

[0008] Methane chemical looping for hydrogen production involves splitting the methane steam reforming process into two or three reactors. Carbon dioxide capture and hydrogen production are performed in different reactors, with the oxygen carrier circulating within each reactor to achieve different reaction processes. However, these different reaction processes have varying requirements for the equilibrium oxygen partial pressure and surface structure of the oxygen carrier. Two-bed or three-bed chemical looping methane production processes based on the same oxygen carrier struggle to simultaneously achieve high CO2 capture rates in the methane oxidation stage and high hydrogen yields in the water-to-hydrogen stage, as well as high methane conversion rates in the methane oxidation stage and high hydrogen purity in the water-to-hydrogen stage. This significantly hinders the industrial application of this chemical looping methane production process.

[0009] In summary, existing chemical chain hydrogen production technologies cannot simultaneously achieve high methane conversion rate, high CO2 capture rate, high hydrogen yield, and high hydrogen purity. Summary of the Invention

[0010] The purpose of this invention is to provide a chemical chain hydrogen production technology for methane that can achieve high methane conversion rate, high CO2 capture rate, high hydrogen yield and high hydrogen purity.

[0011] To address the above problems, the present invention provides the following two technical solutions.

[0012] In a first aspect, the present invention provides a chemical chain reaction hydrogen production system, wherein the system includes a hydrocarbon conversion syngas reactor, a first hydrogen production reactor, a first gas-solid separation device, a syngas oxidation reactor, a second gas-solid separation device, a second hydrogen production reactor, and a third gas-solid separation device.

[0013] The solid product outlet of the hydrocarbon conversion syngas reactor is connected to the solid feed inlet of the first hydrogen production reactor, the product outlet of the first hydrogen production reactor is connected to the feed inlet of the first gas-solid separation device, the gaseous product outlet of the hydrocarbon conversion syngas reactor is connected to the gas feed inlet of the syngas oxidation reactor, the product outlet of the syngas oxidation reactor is connected to the feed inlet of the second gas-solid separation device, the solid product outlet of the second gas-solid separation device is connected to the solid feed inlet of the second hydrogen production reactor, and the product outlet of the second hydrogen production reactor is connected to the feed inlet of the third gas-solid separation device.

[0014] The gas inlet of the hydrocarbon conversion syngas reactor is used for hydrocarbon feed, and the solid inlet of the hydrocarbon conversion syngas reactor is used for oxygen carrier feed; the gas phase product outlet of the first gas-solid separation unit is used for hydrogen discharge; the solid inlet of the syngas oxidation reactor is used for oxygen carrier feed; the gas phase product outlet of the second gas-solid separation unit is used for carbon dioxide discharge; the gas inlet of the first hydrogen production reactor is used for water vapor feed; the gas inlet of the second hydrogen production reactor is used for water vapor feed; and the gas phase product outlet of the third gas-solid separation unit is used for hydrogen discharge.

[0015] According to a preferred embodiment of the first aspect, the first gas-solid separation device includes a cyclone separator and a riser, wherein the solid phase outlet of the cyclone separator is connected to the riser.

[0016] Furthermore, the cyclone separator is located at the top of the riser, the solid phase outlet of the cyclone separator is located at the bottom of the cyclone separator, the gas phase outlet of the first gas-solid separation device is located at the top of the cyclone separator, and the feed inlet of the first gas-solid separation device is located in the middle of the cyclone separator.

[0017] According to a preferred embodiment of the first aspect, the second gas-solid separation device includes a cyclone separator and a riser, wherein the solid phase outlet of the cyclone separator is connected to the riser.

[0018] Furthermore, the cyclone separator is located at the top of the riser, the solid phase outlet of the cyclone separator is located at the bottom of the cyclone separator, the gas phase outlet of the second gas-solid separation device is located at the top of the cyclone separator, and the feed inlet of the second gas-solid separation device is located in the middle of the cyclone separator.

[0019] According to a preferred embodiment of the first aspect, the third gas-solid separation device includes a cyclone separator and a riser, wherein the solid phase outlet of the cyclone separator is connected to the riser.

[0020] Furthermore, the cyclone separator is located at the top of the riser, the solid phase outlet of the cyclone separator is located at the bottom of the cyclone separator, the gas phase outlet of the third gas-solid separation device is located at the top of the cyclone separator, and the feed inlet of the third gas-solid separation device is located in the middle of the cyclone separator.

[0021] According to a preferred embodiment of the first aspect, the chemical looping reaction hydrogen production system further includes a first overflow tank, which is disposed on the connecting pipeline between the solid product outlet of the hydrocarbon conversion syngas reactor and the solid feed inlet of the first hydrogen production reactor.

[0022] According to a preferred embodiment of the first aspect, the chemical looping reaction hydrogen production system further includes a second overflow tank, which is disposed on the connecting pipeline between the solid product outlet of the second gas-solid separation device and the solid feed inlet of the second hydrogen production reactor.

[0023] Furthermore, the second overflow trough is located at the bottom end of the riser of the second gas-solid separation device.

[0024] According to a preferred embodiment of the first aspect, the chemical looping reaction hydrogen production system further includes an oxygen carrier oxidation reactor and a fourth gas-solid separation device.

[0025] The solid product outlet of the first gas-solid separation device is connected to the solid feed inlet of the oxygen carrier oxidation reactor, the product outlet of the oxygen carrier oxidation reactor is connected to the feed inlet of the fourth gas-solid separation device, and the solid product outlet of the fourth gas-solid separation device is connected to the solid feed inlet of the hydrocarbon conversion syngas reactor.

[0026] The gas inlet of the oxygen carrier oxidation reactor is used for feeding oxidizing gases;

[0027] Furthermore, the fourth gas-solid separation device includes a cyclone separator and a riser, wherein the solid phase outlet of the cyclone separator is connected to the riser; further still, the cyclone separator is located at the top of the riser, the solid phase outlet of the cyclone separator is located at the bottom of the cyclone separator, the gas phase outlet of the fourth gas-solid separation device is located at the top of the cyclone separator, and the feed inlet of the fourth gas-solid separation device is located in the middle of the cyclone separator.

[0028] Furthermore, the chemical looping reaction hydrogen production system also includes a third overflow tank, which is located on the connecting pipeline between the solid product outlet of the first gas-solid separation device and the solid feed inlet of the oxygen carrier oxidation reactor; even further, the third overflow tank is located at the bottom end of the riser of the first gas-solid separation device.

[0029] Furthermore, the chemical looping reaction hydrogen production system also includes a fourth overflow tank, which is located on the connecting pipeline between the solid product outlet of the fourth gas-solid separation device and the solid feed inlet of the hydrocarbon conversion syngas reactor; even further, the fourth overflow tank is located at the bottom end of the riser of the fourth gas-solid separation device.

[0030] Furthermore, the oxygen carrier oxidation reactor is selected as a fluidized bed reactor including a main reaction zone and a riser section connected to the material outlet of the main reaction zone. The main reaction zone adopts the form of a bubbling fluidized bed or a turbulent fluidized bed, and the riser section adopts the form of a fast fluidized bed.

[0031] According to a preferred embodiment of the first aspect, the solid product outlet of the third gas-solid separation device is connected to the solid feed inlet of the syngas oxidation reactor.

[0032] According to a preferred embodiment of the first aspect, the chemical looping reaction hydrogen production system further includes a fifth overflow tank, which is disposed on the connecting pipeline between the product outlet of the second hydrogen production reactor and the feed inlet of the third gas-solid separation device.

[0033] Furthermore, the fifth overflow trough is located at the bottom end of the riser of the third gas-solid separation device. According to a preferred embodiment of the first aspect, the syngas oxidation reactor is selected as a fluidized bed reactor comprising a main reaction zone and a riser section connected to the material outlet of the main reaction zone, wherein the main reaction zone adopts a bubbling fluidized bed or a turbulent fluidized bed form, and the riser section adopts a rapid fluidized bed form.

[0034] According to a preferred embodiment of the first aspect, the first hydrogen production reactor is selected as a fluidized bed reactor comprising a main reaction zone and a riser section connected to the material outlet of the main reaction zone, wherein the main reaction zone adopts a bubbling fluidized bed or a turbulent fluidized bed form, and the riser section adopts a rapid fluidized bed form.

[0035] According to a preferred embodiment of the first aspect, the second hydrogen production reactor is selected as a fluidized bed reactor comprising a main reaction zone and a riser section connected to the material outlet of the main reaction zone, wherein the main reaction zone adopts a bubbling fluidized bed or a turbulent fluidized bed form, and the riser section adopts a fast fluidized bed form.

[0036] According to a preferred embodiment of the first aspect, the hydrocarbon conversion syngas reactor is selected as a countercurrent fluidized bed reactor.

[0037] In a second aspect, the present invention provides a chemical chain hydrogen production method, which uses the chemical chain hydrogen production system provided in the first aspect of the present invention, and the method includes:

[0038] Methane and a first oxygen carrier enter a hydrocarbon conversion syngas reactor, where a first reaction takes place to yield syngas as the gaseous product and the reduced first oxygen carrier as the solid product. The first oxygen carrier is selected from those with the chemical formula (Fe2+). 0.3 Ni 0.2 Mn 0.2 Al 0.1 Co 0.2 Oxygen carrier of 3O4;

[0039] The solid product obtained from the first reaction and water vapor enter the first hydrogen production reactor, where they come into contact to carry out the second reaction.

[0040] The product obtained from the second reaction enters the first gas-solid separation device for gas-solid separation, and the gaseous product is hydrogen.

[0041] The gaseous product obtained from the first reaction and the second oxygen carrier enter the syngas oxidation reactor, where the third reaction takes place. The second oxygen carrier is selected from those with the chemical formula LaAl. 1 / 4 Co 1 / 4 Mn 1 / 4 Fe 1 / 4 O3 oxygen carrier;

[0042] The product obtained from the third reaction enters the second gas-solid separation device for gas-solid separation. The gas phase product obtained from the gas-solid separation is CO2, and the solid phase product is the reduced second oxygen carrier.

[0043] The solid product obtained from the second gas-solid separation device and water vapor enter the second hydrogen production reactor, where they come into contact to carry out the fourth reaction.

[0044] The product obtained from the fourth reaction enters the third gas-solid separation unit for gas-solid separation, and the gaseous product is hydrogen.

[0045] According to a preferred embodiment of the second aspect, the chemical looping hydrogen production method further includes:

[0046] The solid product obtained in the first gas-solid separation device (i.e. the reduced first oxygen carrier) and the oxidizing gas enter the oxygen carrier oxidation reactor, where they come into contact to carry out the fifth reaction.

[0047] The product obtained from the fifth reaction enters the fourth gas-solid separation device for gas-solid separation. The solid product obtained from the gas-solid separation is the first oxygen carrier.

[0048] The solid products obtained from the fourth gas-solid separation unit are transported to the hydrocarbon conversion syngas reactor for recycling.

[0049] Furthermore, the solid products obtained in the first gas-solid separation device are treated using the third overflow tank before entering the oxygen carrier oxidation reactor;

[0050] Furthermore, the oxidizing gas is air;

[0051] Furthermore, the temperature of the fifth reaction is 900-1100℃; the pressure of the fifth reaction is 0.1-0.3MPa;

[0052] Furthermore, the method also includes: the solid products obtained from the fourth gas-solid separation device are treated by the fourth overflow tank before being transported to the hydrocarbon conversion syngas reactor for recycling.

[0053] According to a preferred embodiment of the second aspect, the chemical looping hydrogen production method further includes:

[0054] The solid product obtained from the third gas-solid separation unit, namely the second oxygen carrier, is transported to the syngas oxidation reactor for recycling.

[0055] Furthermore, the solid products obtained in the third gas-solid separation unit are treated in the fifth overflow tank before entering the syngas oxidation reactor.

[0056] According to a preferred embodiment of the second aspect, the temperature of the first reaction is 900-1100°C; the pressure of the first reaction is 0.1-0.3 MPa.

[0057] According to a preferred embodiment of the second aspect, the ratio of methane to the first oxygen carrier is 1-3 mL: 1 g.

[0058] According to a preferred embodiment of the second aspect, the temperature of the second reaction is 800-900°C; the pressure of the second reaction is 0.1-0.3 MPa.

[0059] According to a preferred embodiment of the second aspect, in the first hydrogen production reactor, the ratio of water vapor to the solid product obtained from the first reaction is 5-10 mL: 1 g.

[0060] According to a preferred embodiment of the second aspect, the temperature of the third reaction is 850-950°C; the pressure of the third reaction is 0.1-0.3 MPa.

[0061] According to a preferred embodiment of the second aspect, in the syngas oxidation reactor, the ratio of the gaseous product obtained from the first reaction to the second oxygen carrier is 1-3 mL: 1 g.

[0062] According to a preferred embodiment of the second aspect, the temperature of the fourth reaction is 900-1100°C; the pressure of the fourth reaction is 0.1-0.3 MPa.

[0063] According to a preferred embodiment of the second aspect, in the second hydrogen production reactor, the ratio of water vapor to the solid product obtained from the second gas-solid separation device is 5-10 mL: 1 g.

[0064] According to a preferred embodiment of the second aspect, the solid product obtained from the first reaction is treated using a first overflow tank before entering the first hydrogen production reactor.

[0065] According to a preferred embodiment of the second aspect, the solid product obtained from the second gas-solid separation device is first treated using a second overflow tank before entering the second hydrogen production reactor.

[0066] The technical solution provided by this invention can simultaneously achieve high methane conversion rate, high CO2 capture rate, high hydrogen yield, and high hydrogen purity. Compared with the prior art, the technical solution provided by this invention has the following beneficial effects:

[0067] 1. The chemical chain hydrogen production technology provided by this invention is based on two special oxygen carriers that are independently recycled, achieving efficient conversion of methane to syngas and hydrogen production from syngas while simultaneously capturing carbon dioxide. This effectively improves the compatibility between different reactions. Furthermore, the dual hydrogen production unit design fully utilizes the reduced oxygen vacancies in the metal oxygen carrier, thereby increasing the hydrogen yield.

[0068] 2. The chemical chaining hydrogen production technology provided by this invention separates the thermodynamically incompatible processes of complete methane conversion to carbon dioxide (achieving carbon capture) and steam hydrogen production into two relatively independent units: partial methane oxidation and syngas hydrogen production. A multi-bed combined chemical chaining reaction system is used to achieve the complete methane conversion, carbon dioxide capture, and hydrogen production processes. The methane conversion section serves as a connecting bridge between the two units, dividing the methane conversion process into two reaction units. The first unit mainly involves the partial oxidation of methane, using a suitable amount of metallic Ni and a moderate equilibrium oxygen partial pressure (pO2 = 10). -22 -10 -17 ) of (Fe 0.3 Ni 0.2 Mn 0.2 Al 0.1 Co 0.2The 3O4 high-entropy spinel oxygen carrier converts methane into syngas, followed by gas-solid separation. The oxygen carrier then enters the steam reforming unit to produce hydrogen. The syngas produced in the first unit enters the syngas reforming reactor in the second unit, where the main process is the further oxidation of the syngas, using a reactor with a moderate equilibrium oxygen partial pressure (pO2 = 10). -19 -10 -16 ) of LaAl 1 / 4 Co 1 / 4 Mn 1 / 4 Fe 1 / 4 The entropy-medium perovskite in O3 and the oxygen carrier, which can be partially or completely oxidized by water vapor after reduction, convert syngas into carbon dioxide and water. High-purity carbon dioxide can then be obtained through condensation, achieving carbon capture. The oxygen carrier, after gas-solid separation, enters the steam reforming unit to produce hydrogen. By introducing water-to-hydrogen processes into both the methane partial oxidation to syngas unit and the syngas oxidation for efficient CO2 capture unit, the utilization rate of lattice oxygen is improved, thereby increasing the hydrogen yield.

[0069] 3. The chemical chain hydrogen production technology provided by this invention incorporates steam reactors in both the methane conversion unit and the hydrogen production unit. After methane conversion in the first unit, the partially or completely reduced oxygen carrier enters the steam hydrogen production reactor to produce hydrogen. In the syngas conversion unit, carbon dioxide is captured while simultaneously yielding more hydrogen. This fully utilizes the lattice oxygen in the oxygen carrier, increasing the hydrogen yield. The chemical chain hydrogen production technology provided by this invention can simultaneously achieve carbon dioxide capture and high-yield hydrogen production.

[0070] 4. The chemical chain hydrogen production technology solution provided by this invention can realize the continuous circulation operation of the oxygen carrier, which is beneficial to the operation of large-scale industrial plants.

[0071] 5. The chemical chain hydrogen production technology provided by this invention splits the chemical chain hydrogen production coupled with CO2 capture process into two relatively independent units: methane to syngas production and syngas to hydrogen production. Compared with the oxygen carrier in the traditional three-bed chemical chain hydrogen production process that simultaneously couples CO2, an oxygen carrier with a lower equilibrium oxygen partial pressure suitable for steam oxidation to produce hydrogen can be selected, which can increase hydrogen production. Simultaneously, by utilizing the different activation processes of methane and carbon monoxide, and by constructing suitable CH bond activation sites in the methane to syngas unit and designing an oxygen carrier with moderate CO adsorption capacity in the syngas to hydrogen stage, efficient methane conversion and improved hydrogen purity can be achieved. Attached Figure Description

[0072] Figure 1 This is a schematic diagram of the chemical chain hydrogen production system in Example 1. Detailed Implementation

[0073] In order to provide a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention will now be described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.

[0074] Example 1

[0075] This embodiment provides a chemical chain hydrogen production system.

[0076] like Figure 1 As shown, the system includes: an oxygen carrier oxidation reactor 1, a first hydrogen production reactor 2, a hydrocarbon conversion syngas reactor 3, a second hydrogen production reactor 4, a syngas oxidation reactor 5, a first overflow tank 12, a second overflow tank 14, a third overflow tank 10, a fourth overflow tank 11, a fifth overflow tank 13, a first gas-solid separation device 6, a second gas-solid separation device 9, a third gas-solid separation device 8, and a fourth gas-solid separation device 7.

[0077] The first gas-solid separation device 6 includes a cyclone separator and a riser. The cyclone separator is located at the top of the riser, and the solid phase outlet at the bottom of the cyclone separator is connected to the top of the riser. The feed inlet of the first gas-solid separation device 6 is located in the middle of the cyclone separator, the gas phase outlet of the first gas-solid separation device 6 is located at the top of the cyclone separator, and the solid phase outlet of the first gas-solid separation device 6 is located at the bottom of the riser. The fourth gas-solid separation device 7 also includes a cyclone separator and a riser. The cyclone separator is located at the top of the riser, and the solid phase outlet at the bottom of the cyclone separator is connected to the top of the riser. The feed inlet of the fourth gas-solid separation device 7 is located in the middle of the cyclone separator, and the gas phase outlet of the fourth gas-solid separation device 7 is located at the bottom of the cyclone separator. At the top, the solid outlet of the fourth gas-solid separation device 7 is located at the bottom of the riser; the solid product outlet of the hydrocarbon conversion syngas reactor 3 is connected to the feed inlet of the first hydrogen production reactor 2; the first overflow tank 12 is located on the connecting pipeline between the solid product outlet of the hydrocarbon conversion syngas reactor 3 and the feed inlet of the first hydrogen production reactor 2; the product outlet of the first hydrogen production reactor 2 is connected to the feed inlet of the first gas-solid separation device 6; the solid product outlet of the first gas-solid separation device 6 is connected to the solid feed inlet of the oxygen carrier oxidation reactor 1; and the third overflow tank 10 is located between the solid product outlet of the first gas-solid separation device 6 and the solid feed inlet of the oxygen carrier oxidation reactor 1. The connecting pipeline is specifically located at the bottom end of the riser of the first gas-solid separation device 6. The product outlet of the oxygen carrier oxidation reactor 1 is connected to the inlet of the fourth gas-solid separation device 7. The solid product outlet of the fourth gas-solid separation device 7 is connected to the solid inlet of the hydrocarbon conversion syngas reactor 3. The fourth overflow tank 11 is located on the connecting pipeline between the solid product outlet of the fourth gas-solid separation device 7 and the solid inlet of the hydrocarbon conversion syngas reactor 3, specifically at the bottom end of the riser of the fourth gas-solid separation device 7. The gas inlet of the hydrocarbon conversion syngas reactor 3 is used for hydrocarbon feeding, and the gas inlet of the oxygen carrier oxidation reactor 1 is used for oxidizing... For gas feeding, the first overflow tank 12, the third overflow tank 10, and the fourth overflow tank 11 are all equipped with water vapor loosening air inlets; the oxygen carrier oxidation reactor 1 is a fluidized bed reactor including a main reaction zone and a riser section connected to the material outlet of the main reaction zone, wherein the main reaction zone adopts the form of a bubbling fluidized bed or a turbulent fluidized bed, and the riser section adopts the form of a fast fluidized bed; the first hydrogen production reactor 2 is a fluidized bed reactor including a main reaction zone and a riser section connected to the material outlet of the main reaction zone, wherein the main reaction zone adopts the form of a bubbling fluidized bed or a turbulent fluidized bed, and the riser section adopts the form of a fast fluidized bed; the hydrocarbon conversion syngas reactor 3 is a countercurrent fluidized bed reactor.

[0078] The second gas-solid separation device 9 includes a cyclone separator and a riser. The cyclone separator is located at the top of the riser, and the solid phase outlet at the bottom of the cyclone separator is connected to the top of the riser. The feed inlet of the second gas-solid separation device 9 is located in the middle of the cyclone separator, the gas phase outlet of the second gas-solid separation device 9 is located at the top of the cyclone separator, and the solid phase outlet of the second gas-solid separation device 9 is located at the bottom of the riser. The third gas-solid separation device 8 includes a cyclone separator and a riser. The cyclone separator is located at the top of the riser, and the solid phase outlet at the bottom of the cyclone separator is connected to the top of the riser. The feed inlet of the third gas-solid separation device 8 is located in the middle of the cyclone separator. The gas phase outlet of the gas-solid separation device 8 is located at the top of the cyclone separator, and the solid phase outlet of the third gas-solid separation device 8 is located at the bottom of the riser. The gas phase product outlet of the hydrocarbon conversion syngas reactor 3 is connected to the gas inlet of the syngas oxidation reactor 5, the product outlet of the syngas oxidation reactor 5 is connected to the inlet of the second gas-solid separation device 9, the solid phase product outlet of the second gas-solid separation device 9 is connected to the solid inlet of the second hydrogen production reactor 4, and the second overflow tank 14 is located on the connecting pipeline between the solid phase product outlet of the second gas-solid separation device 9 and the solid inlet of the second hydrogen production reactor 4. The product outlet of the second hydrogen production reactor 4 is connected to the feed inlet of the third gas-solid separation device 8, and the solid product outlet of the third gas-solid separation device 8 is connected to the solid feed inlet of the syngas oxidation reactor 5. The fifth overflow tank 13 is located on the connecting pipeline between the solid product outlet of the third gas-solid separation device 8 and the solid feed inlet of the syngas oxidation reactor 5, specifically at the bottom of the riser of the third gas-solid separation device 8. The syngas oxidation reactor 5 is a fluidized bed reactor comprising a main reaction zone and a riser section connected to the material outlet of the main reaction zone. The main reaction zone adopts... The second hydrogen production reactor 4 is a fluidized bed reactor consisting of a main reaction zone and a riser section connected to the material outlet of the main reaction zone. The main reaction zone is a bubbling fluidized bed or a turbulent fluidized bed, and the riser section is a fast fluidized bed. The gas phase product outlet of the second gas-solid separation device 9 is used to discharge carbon dioxide, the gas inlet of the second hydrogen production reactor 4 is used to feed water vapor, the gas phase product outlet of the third gas-solid separation device 8 is used to discharge hydrogen, and the second overflow tank 14 and the fifth overflow tank 13 are both equipped with water vapor loosening air inlets.

[0079] Example 2

[0080] This embodiment provides a chemical chain hydrogen production method.

[0081] This method is carried out using the chemical chain hydrogen production system provided in Example 1, and the method includes:

[0082] 1) Methane and the first oxygen carrier enter the hydrocarbon conversion syngas reactor 3, where they undergo a first reaction in counter-current flow contact; wherein, the first oxygen carrier is selected with the chemical formula (Fe... 0.3 Ni 0.2 Mn 0.2 Al 0.1 Co 0.2 Oxygen carrier of 3O4;

[0083] The first oxygen carrier can be prepared through the following process:

[0084] (1) Anhydrous citric acid is dissolved in deionized water to obtain an aqueous solution of citric acid; according to (Fe 0.3 Ni 0.2 Mn 0.2 Al 0.1 Co 0.2 The stoichiometric ratio of Fe, Ni, Mn, Co, and Al in NO3O4 was determined by weighing out Fe(NO3)3·9H2O, Ni(NO3)2·6H2O, Mn(NO3)2 aqueous solution, Co(NO3)2·6H2O, and Al(NO3)3·9H2O, and dissolving them in citric acid aqueous solution to prepare a precursor solution, wherein the molar ratio of anhydrous citric acid to the total amount of metal ions was 1.2:1.

[0085] (2) The precursor solution was evaporated to a gel state under stirring; then aged in a 130°C constant temperature drying oven for 12 hours to obtain precursor powder; the obtained precursor powder was calcined at 900°C in air for 4 hours to obtain the first oxygen carrier (Fe). 0.3 Ni 0.2 Mn 0.2 Al 0.1 Co 0.2 )3O4.

[0086] The temperature of the first reaction is 1000℃; the pressure of the first reaction is atmospheric pressure.

[0087] The methane feed rate is 6000 mL / min, and the first oxygen carrier feed rate is 3000 g / min.

[0088] 2) The solid product obtained from the first reaction in the hydrocarbon conversion syngas reactor 3 is treated by the first overflow tank 12 and then enters the first hydrogen production reactor 2 with water vapor. The second reaction is carried out in the first hydrogen production reactor 2 (including the reaction of the reduced first oxygen carrier with air in the main reaction zone in the form of a bubbling fluidized bed, and then entering the riser section in the form of a fast fluidized bed to continue the reaction).

[0089] The second reaction is carried out at a temperature of 900℃ and a pressure of atmospheric pressure.

[0090] In the first hydrogen production reactor 2, the steam feed rate is 30,000 mL / min.

[0091] 3) The product obtained from the second reaction enters the first gas-solid separation device 6 for gas-solid separation, and the gas phase product is hydrogen and the solid phase product is the first oxygen carrier after partial oxidation; the gas phase product hydrogen is collected after condensation.

[0092] 4) The solid product obtained in the first gas-solid separation device 6 is treated by the third overflow tank 10 and then enters the oxygen carrier oxidation reactor 1 with the oxidizing gas air. The fifth reaction is carried out in the oxygen carrier oxidation reactor 1 (including the reaction of the reduced first oxygen carrier with air in the main reaction zone in the form of a bubbling fluidized bed, and then entering the riser section in the form of a fast fluidized bed to continue the reaction). The product obtained from the fifth reaction enters the fourth gas-solid separation device 7 for gas-solid separation. The solid product obtained from the gas-solid separation is the first oxygen carrier. The first oxygen carrier obtained from the fourth gas-solid separation device 7 is treated by the fourth overflow tank 11 and then transported to the hydrocarbon conversion syngas reactor 3 for recycling.

[0093] The fifth reaction is carried out at a temperature of 1000℃ and a pressure of atmospheric pressure.

[0094] The feed rate of the oxidizing gas air is 12000 mL / min.

[0095] 5) The gaseous products obtained from the first reaction in the hydrocarbon conversion syngas reactor 3 and the second oxygen carrier enter the syngas oxidation reactor 5, where a third reaction takes place (including the reaction of the gaseous products obtained from the first reaction and the second oxygen carrier in the main reaction zone using a bubbling fluidized bed, followed by further reaction in the riser section using a rapid fluidized bed). The second oxygen carrier is selected from those with the chemical formula LaAl. 1 / 4 Co 1 / 4 Mn 1 / 4 Fe 1 / Oxygen carrier of 4O3;

[0096] The second oxygen carrier can be prepared through the following process:

[0097] (1) Anhydrous citric acid is dissolved in deionized water to obtain an aqueous solution of citric acid; according to LaAl 1 / 4 Co 1 / 4 Mn 1 / 4 Fe 1 / The stoichiometric ratio of La, Al, Co, Mn, and Fe in 4O3 was determined by weighing out aqueous solutions of La(NO3)3·6H2O, Al(NO3)3·9H2O, Co(NO3)2·6H2O, Mn(NO3)2, and Fe(NO3)3·9H2O, and dissolving them in an aqueous solution of citric acid to prepare a precursor solution, wherein the molar ratio of anhydrous citric acid to the total amount of metal ions was 1.2:1.

[0098] (2) The precursor solution was evaporated to a gel state under stirring; then aged in a 130°C constant temperature drying oven for 12 hours to obtain precursor powder; the obtained precursor powder was calcined at 900°C in air atmosphere for 4 hours to obtain the second oxygen carrier LaAl. 1 / 4 Co 1 / 4 Mn 1 / 4 Fe 1 / 4 O3.

[0099] The temperature of the third reaction is 900℃; the pressure of the third reaction is atmospheric pressure.

[0100] In the synthesis gas oxidation reactor 5, the rate of synthesis gas entering is approximately 18,000 mL / min, and the feed rate of the second oxygen carrier is 9,000 g / min.

[0101] 6) The product obtained from the third reaction enters the second gas-solid separation device 9 for gas-solid separation. The gas phase product obtained from the gas-solid separation is CO2, and the solid phase product is the reduced second oxygen carrier. The gas phase product CO2 is condensed and dehydrated for CO2 capture.

[0102] 7) The solid product obtained from the second gas-solid separation device 9 is treated by the second overflow tank 14 and then enters the second hydrogen production reactor 4 with water vapor. The fourth reaction is carried out in the second hydrogen production reactor 4 (including the reaction of the solid product obtained from the second gas-solid separation device 9, i.e. the reduced second oxygen carrier, with water vapor in the main reaction zone of the bubbling fluidized bed form, and then entering the riser section of the rapid fluidized bed form to continue the reaction).

[0103] The temperature of the fourth reaction is 1000℃; the pressure of the fourth reaction is atmospheric pressure.

[0104] The feed rate of water vapor in the second hydrogen production reactor is 54,000 mL / min.

[0105] 8) The product obtained from the fourth reaction enters the third gas-solid separation device 8 for gas-solid separation, and the gas phase product is hydrogen and the solid phase product is the second oxygen carrier; the gas phase product hydrogen is collected after condensation.

[0106] 9) The solid product, the second oxygen carrier, obtained in the third gas-solid separation device 8 is processed by the fifth overflow tank 13 and then transported to the synthesis gas oxidation reactor 5 for recycling.

[0107] Example 3

[0108] This embodiment provides a chemical chain hydrogen production method.

[0109] This method is carried out using the chemical chain hydrogen production system provided in Example 1, and the method includes:

[0110] 1) Methane and the first oxygen carrier enter the hydrocarbon conversion syngas reactor 3, where they undergo a first reaction in counter-current flow contact; wherein, the first oxygen carrier is selected with the chemical formula (Fe... 0.3 Ni 0.2 Mn 0.2 Al 0.1 Co 0.2 Oxygen carrier of 3O4;

[0111] The temperature of the first reaction is 900℃; the pressure of the first reaction is atmospheric pressure.

[0112] The methane feed rate is 3200 mL / min, and the first oxygen carrier feed rate is 3000 g / min.

[0113] 2) The solid product obtained from the first reaction in the hydrocarbon conversion syngas reactor 3 is treated by the first overflow tank 12 and then enters the first hydrogen production reactor 2 with water vapor. The second reaction is carried out in the first hydrogen production reactor 2 (including the reaction of the reduced first oxygen carrier with air in the main reaction zone in the form of a bubbling fluidized bed, and then entering the riser section in the form of a fast fluidized bed to continue the reaction).

[0114] The second reaction is carried out at a temperature of 800℃ and a pressure of atmospheric pressure.

[0115] In the first hydrogen production reactor 2, the steam feed rate is 18000 mL / min.

[0116] 3) The product obtained from the second reaction enters the first gas-solid separation device 6 for gas-solid separation, and the gas phase product is hydrogen and the solid phase product is the first oxygen carrier after partial oxidation; the gas phase product hydrogen is collected after condensation.

[0117] 4) The solid product obtained in the first gas-solid separation device 6 is treated by the third overflow tank 10 and then enters the oxygen carrier oxidation reactor 1 with the oxidizing gas air. The fifth reaction is carried out in the oxygen carrier oxidation reactor 1 (including the reaction of the reduced first oxygen carrier with air in the main reaction zone in the form of a bubbling fluidized bed, and then entering the riser section in the form of a fast fluidized bed to continue the reaction). The product obtained from the fifth reaction enters the fourth gas-solid separation device 7 for gas-solid separation. The solid product obtained from the gas-solid separation is the first oxygen carrier. The first oxygen carrier obtained from the fourth gas-solid separation device 7 is treated by the fourth overflow tank 11 and then transported to the hydrocarbon conversion syngas reactor 3 for recycling.

[0118] The fifth reaction is carried out at a temperature of 900℃ and a pressure of atmospheric pressure.

[0119] The feed rate of the oxidizing gas air is 15000 mL / min.

[0120] 5) The gaseous products obtained from the first reaction in the hydrocarbon conversion syngas reactor 3 and the second oxygen carrier enter the syngas oxidation reactor 5, where a third reaction takes place (including the reaction of the gaseous products obtained from the first reaction and the second oxygen carrier in the main reaction zone using a bubbling fluidized bed, followed by further reaction in the riser section using a rapid fluidized bed). The second oxygen carrier is selected from those with the chemical formula LaAl. 1 / 4 Co 1 / 4 Mn 1 / 4 Fe 1 / Oxygen carrier of 4O3;

[0121] The temperature of the third reaction is 950℃; the pressure of the third reaction is atmospheric pressure.

[0122] The syngas entering the syngas oxidation reactor 5 is approximately 18,000 mL / min, and the feed rate of the second oxygen carrier is 6,000 g / min.

[0123] 6) The product obtained from the third reaction enters the second gas-solid separation device 9 for gas-solid separation. The gas phase product obtained from the gas-solid separation is CO2, and the solid phase product is the reduced second oxygen carrier. The gas phase product CO2 is condensed and dehydrated for CO2 capture.

[0124] 7) The solid product obtained from the second gas-solid separation device 9 is treated by the second overflow tank 14 and then enters the second hydrogen production reactor 4 with water vapor. The fourth reaction is carried out in the second hydrogen production reactor 4 (including the reaction of the solid product obtained from the second gas-solid separation device 9, i.e. the reduced second oxygen carrier, with water vapor in the main reaction zone of the bubbling fluidized bed form, and then entering the riser section of the rapid fluidized bed form to continue the reaction).

[0125] The temperature of the fourth reaction is 1050℃; the pressure of the fourth reaction is atmospheric pressure.

[0126] The feed rate of water vapor in the second hydrogen production reactor is 36,000 mL / min.

[0127] 8) The product obtained from the fourth reaction enters the third gas-solid separation device 8 for gas-solid separation, and the gas phase product is hydrogen and the solid phase product is the second oxygen carrier; the gas phase product hydrogen is collected after condensation.

[0128] 9) The solid product, the second oxygen carrier, obtained in the third gas-solid separation device 8 is processed by the fifth overflow tank 13 and then transported to the synthesis gas oxidation reactor 5 for recycling.

[0129] Comparative Example 1

[0130] This comparative example provides a chemical chain hydrogen production method.

[0131] This method uses a three-bed circulating fluidized bed chemical chain hydrogen production system. Compared with the chemical chain hydrogen production system provided in Example 1, the three-bed circulating fluidized bed chemical chain hydrogen production system does not include the oxygen carrier oxidation reactor 1, the first hydrogen production reactor 2, the hydrocarbon conversion syngas reactor 3, the first overflow tank 12, the third overflow tank 10, the fourth overflow tank 11, the first gas-solid separation device 6, and the fourth gas-solid separation device 7.

[0132] Compared with the chemical chain hydrogen production method provided in Example 2, this method does not include steps 1)-4), and in step 5), the gas entering the syngas oxidation reactor 5 is not syngas (i.e. the gaseous product obtained from the first reaction in the hydrocarbon conversion syngas reactor 3) but methane, and the methane feed rate is the same as the methane feed rate in Example 2.

[0133] Comparative Example 2

[0134] This comparative example provides a chemical chain hydrogen production method.

[0135] The difference between this method and Example 3 is that both the first and second oxygen carriers are Fe2WO6.

[0136] The CH4 conversion, CO2 selectivity, H2 yield, and H2 purity of each embodiment and comparative example are shown in Table 1 below.

[0137] Table 1

[0138] Serial Number <![CDATA[CH4 conversion rate (%)]]> <![CDATA[CO2 selectivity (%)]]> <![CDATA[H2 production rate mmol / g]]> <![CDATA[H2 purity (%)]]> Example 2 64 95 2.8 99.2 Example 3 66 96 2.7 99.5 Comparative Example 1 57 85 1.9 93.4 Comparative Example 2 58 88 1.1 86.1

[0139] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A chemical loop reaction hydrogen production system, wherein, The system includes a hydrocarbon conversion syngas reactor, a first hydrogen production reactor, a first gas-solid separation device, a syngas oxidation reactor, a second gas-solid separation device, a second hydrogen production reactor, and a third gas-solid separation device; The solid product outlet of the hydrocarbon conversion syngas reactor is connected to the solid feed inlet of the first hydrogen production reactor, the product outlet of the first hydrogen production reactor is connected to the feed inlet of the first gas-solid separation device, the gaseous product outlet of the hydrocarbon conversion syngas reactor is connected to the gas feed inlet of the syngas oxidation reactor, the product outlet of the syngas oxidation reactor is connected to the feed inlet of the second gas-solid separation device, the solid product outlet of the second gas-solid separation device is connected to the solid feed inlet of the second hydrogen production reactor, and the product outlet of the second hydrogen production reactor is connected to the feed inlet of the third gas-solid separation device. The gas inlet of the hydrocarbon conversion syngas reactor is used for hydrocarbon feed, and the solid inlet of the hydrocarbon conversion syngas reactor and the syngas oxidation reactor is used for oxygen carrier feed; the gas phase product outlet of the first gas-solid separation device and the third gas-solid separation device is used for hydrogen discharge; the gas phase product outlet of the second gas-solid separation device is used for carbon dioxide discharge; and the gas inlet of the first hydrogen production reactor and the second hydrogen production reactor is used for water vapor feed.

2. The system according to claim 1, wherein, The first gas-solid separation device includes a cyclone separator and a riser, wherein the solid phase outlet of the cyclone separator is connected to the riser; and / or The second gas-solid separation unit includes a cyclone separator and a riser, wherein the solid phase outlet of the cyclone separator is connected to the riser; and / or The third gas-solid separation equipment includes a cyclone separator and a riser, wherein the solid phase outlet of the cyclone separator is connected to the riser.

3. The system according to claim 1, wherein, The chemical looping reaction hydrogen production system also includes an oxygen carrier oxidation reactor and a fourth gas-solid separation unit; The solid product outlet of the first gas-solid separation device is connected to the solid feed inlet of the oxygen carrier oxidation reactor, the product outlet of the oxygen carrier oxidation reactor is connected to the feed inlet of the fourth gas-solid separation device, and the solid product outlet of the fourth gas-solid separation device is connected to the solid feed inlet of the hydrocarbon conversion syngas reactor. The gas inlet of the oxygen carrier oxidation reactor is used for feeding oxidizing gases.

4. The system according to claim 3, wherein, The fourth gas-solid separation unit includes a cyclone separator and a riser, wherein the solid phase outlet of the cyclone separator is connected to the riser; and / or The oxygen carrier oxidation reactor is a fluidized bed reactor consisting of a main reaction zone and a riser section connected to the material outlet of the main reaction zone. The main reaction zone adopts a bubbling fluidized bed or a turbulent fluidized bed, and the riser section adopts a fast fluidized bed.

5. The system according to claim 1, wherein, The solid product outlet of the third gas-solid separation unit is connected to the solid feed inlet of the syngas oxidation reactor.

6. The system according to claim 1, wherein, The first hydrogen production reactor is a fluidized bed reactor comprising a main reaction zone and a riser section connected to the material outlet of the main reaction zone. The main reaction zone employs a bubbling fluidized bed or a turbulent fluidized bed configuration, and the riser section employs a rapid fluidized bed configuration; and / or The second hydrogen production reactor is a fluidized bed reactor comprising a main reaction zone and a riser section connected to the material outlet of the main reaction zone. The main reaction zone employs a bubbling fluidized bed or a turbulent fluidized bed, and the riser section employs a rapid fluidized bed; and / or The hydrocarbon conversion syngas reactor is a countercurrent fluidized bed reactor.

7. A chemical looping hydrogen production method, wherein the method is carried out using the chemical looping hydrogen production system according to any one of claims 1-6, the method comprising: Methane and a first oxygen carrier enter a hydrocarbon conversion syngas reactor, where a first reaction takes place to yield syngas as the gaseous product and the reduced first oxygen carrier as the solid product. The first oxygen carrier is selected from those with the chemical formula (Fe2+). 0.3 Ni 0.2 Mn 0.2 Al 0.1 Co 0.2 Oxygen carrier of 3O4; The solid product obtained from the first reaction and water vapor enter the first hydrogen production reactor, where they come into contact to carry out the second reaction. The product obtained from the second reaction enters the first gas-solid separation device for gas-solid separation, and the gaseous product is hydrogen. The gaseous product obtained from the first reaction and the second oxygen carrier enter the syngas oxidation reactor, where the third reaction takes place. The second oxygen carrier is selected from those with the chemical formula LaAl. 1 / 4 Co 1 / 4 Mn 1 / 4 Fe 1 / 4 O3 oxygen carrier; The product obtained from the third reaction enters the second gas-solid separation device for gas-solid separation. The gas phase product obtained from the gas-solid separation is CO2, and the solid phase product is the reduced second oxygen carrier. The solid product obtained from the second gas-solid separation device and water vapor enter the second hydrogen production reactor, where they come into contact to carry out the fourth reaction. The product obtained from the fourth reaction enters the third gas-solid separation unit for gas-solid separation, and the gaseous product is hydrogen.

8. The method according to claim 7, wherein, Chemical chain hydrogen production methods also include: The solid product obtained in the first gas-solid separation device and the oxidizing gas enter the oxygen carrier oxidation reactor, where they come into contact to carry out the fifth reaction. The product obtained from the fifth reaction enters the fourth gas-solid separation device for gas-solid separation. The solid product obtained from the gas-solid separation is the first oxygen carrier. The solid products obtained from the fourth gas-solid separation unit are transported to the hydrocarbon conversion syngas reactor for recycling.

9. The method according to claim 7, wherein, The oxidizing gas is air; and / or The temperature of the fifth reaction is 900-1100℃; the pressure of the fifth reaction is 0.1-0.3MPa.

10. The method according to claim 7, wherein, Chemical chain hydrogen production methods also include: The solid product obtained from the third gas-solid separation unit, namely the second oxygen carrier, is transported to the syngas oxidation reactor for recycling.

11. The method according to claim 7, wherein, The temperature of the first reaction is 900-1100℃; the pressure of the first reaction is 0.1-0.3MPa; and / or The ratio of methane to the first oxygen carrier is 1-3 mL: 1 g.

12. The method according to claim 7, wherein, The temperature of the second reaction is 800-900℃; the pressure of the second reaction is 0.1-0.3 MPa; and / or In the first hydrogen production reactor, the ratio of water vapor to the solid product obtained from the first reaction is 5-10 mL: 1 g.

13. The method according to claim 7, wherein, The temperature of the third reaction is 850-950℃; the pressure of the third reaction is 0.1-0.3 MPa; and / or In the syngas oxidation reactor, the ratio of the gaseous product obtained from the first reaction to the second oxygen carrier is 1-3 mL: 1 g.

14. The method according to claim 7, wherein, The temperature of the fourth reaction is 900-1100℃; the pressure of the fourth reaction is 0.1-0.3 MPa; and / or In the second hydrogen production reactor, the ratio of water vapor to the solid product obtained from the second gas-solid separation device is 5-10 mL: 1 g.

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