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 gas-solid separation device, a syngas oxidation reactor, a second gas-solid separation device, a hydrogen production reactor and a third gas-solid separation device; the product outlet of the hydrocarbon conversion syngas reactor is connected with the feed inlet of the first gas-solid separation device, the gas phase product outlet of the first gas-solid separation device is connected with the gas feed inlet of the syngas oxidation reactor, the gas phase product outlet of the syngas oxidation reactor is connected with the feed inlet of the second gas-solid separation device, the solid phase product outlet of the syngas oxidation reactor is connected with the solid feed inlet of the hydrogen production reactor, and the product outlet of the hydrogen production reactor is connected with the feed inlet of the third gas-solid separation device. The technical scheme provided by the application can realize continuous methane efficient conversion, carbon dioxide capture and high hydrogen production rate and hydrogen purity.

Description

Technical Field

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

[0002] Hydrogen is a highly efficient and clean energy source that produces no pollutants during use, making it environmentally friendly. Currently, the most mainstream hydrogen production technology is fossil fuel combustion and conversion, which emits large amounts of carbon dioxide, impacting the environment. Chemical looping hydrogen production technology, as a highly efficient fuel conversion technology, effectively avoids carbon dioxide emissions. Chemical looping hydrogen production technology produces high-purity hydrogen without requiring product separation steps, meeting the development needs of hydrogen production technology.

[0003] Chemical looping of methane for hydrogen production involves splitting the methane steam reforming process into two or three reactors. Carbon dioxide capture and hydrogen production are carried out separately in each reactor, with the oxygen carrier circulating among them to achieve different reaction processes. Currently, chemical looping for hydrogen production is still in the laboratory research stage, and there are no reports of industrial-scale applications.

[0004] 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.

[0005] 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.

[0006] 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.

[0007] In summary, existing chemical chain hydrogen production technologies struggle to achieve both high hydrogen yield and purity while continuously and efficiently converting methane and capturing carbon dioxide. Summary of the Invention

[0008] The purpose of this invention is to provide a chemical chain hydrogen production technology for methane that can simultaneously achieve efficient continuous methane conversion, carbon dioxide capture, high hydrogen yield, and high hydrogen purity.

[0009] To address the above problems, the present invention provides the following two technical solutions.

[0010] In a first aspect, the present invention provides a chemical loop reaction hydrogen production system, wherein the system includes a hydrocarbon conversion syngas reactor, a first gas-solid separation device, a syngas oxidation reactor, a second gas-solid separation device, a hydrogen production reactor, and a third gas-solid separation device.

[0011] The product outlet of the hydrocarbon conversion syngas reactor is connected to the inlet of the first gas-solid separation device; the gas phase product outlet of the first gas-solid separation device is connected to the gas inlet of the syngas oxidation reactor; the gas phase product outlet of the syngas oxidation reactor is connected to the inlet of the second gas-solid separation device; the solid phase product outlet of the syngas oxidation reactor is connected to the solid inlet of the hydrogen production reactor; and the product outlet of the hydrogen production reactor is connected to the inlet of the third gas-solid separation device.

[0012] 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 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 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.

[0013] 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 gas phase product outlet of the syngas oxidation reactor and the feed inlet of the second gas-solid separation device.

[0014] 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 syngas oxidation reactor and the solid feed inlet of the hydrogen production reactor.

[0015] According to a preferred embodiment of the first aspect, the chemical looping reaction hydrogen production system further includes a first oxygen carrier oxidation reactor and a fourth gas-solid separation device.

[0016] The solid product outlet of the first gas-solid separation device is connected to the solid feed inlet of the first oxygen carrier oxidation reactor, the product outlet of the first 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.

[0017] The gas inlet of the first oxygen carrier oxidation reactor is used for feeding oxidizing gas;

[0018] 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 first oxygen carrier oxidation reactor.

[0019] 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.

[0020] Furthermore, the first 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, 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;

[0021] 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.

[0022] According to a preferred embodiment of the first aspect, the chemical looping reaction hydrogen production system further includes a second oxygen carrier oxidation reactor and a fifth gas-solid separation device.

[0023] The solid product outlet of the second gas-solid separation device is connected to the solid feed inlet of the second oxygen carrier oxidation reactor; the solid product outlet of the third gas-solid separation device is connected to the solid feed inlet of the second oxygen carrier oxidation reactor; the product outlet of the second oxygen carrier oxidation reactor is connected to the feed inlet of the fifth gas-solid separation device; and the gaseous product outlet of the fifth gas-solid separation device is connected to the solid feed inlet of the syngas oxidation reactor.

[0024] The gas inlet of the second oxygen carrier oxidation reactor is used for feeding oxidizing gas;

[0025] Furthermore, the chemical looping reaction hydrogen production system also includes a fifth overflow tank, which is located on the connecting pipeline between the solid product outlet of the third gas-solid separation device and the solid feed inlet of the second oxygen carrier oxidation reactor.

[0026] Furthermore, the chemical looping reaction hydrogen production system also includes a sixth overflow tank, which is located on the connecting pipeline between the solid product outlet of the fifth gas-solid separation unit and the solid feed inlet of the syngas oxidation reactor.

[0027] Furthermore, the second oxygen carrier oxidation 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, 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;

[0028] Furthermore, the fifth 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.

[0029] According to a preferred embodiment of the first aspect, the hydrocarbon conversion syngas 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, 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.

[0030] According to a preferred embodiment of the first aspect, the hydrogen production 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, 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.

[0031] According to a preferred embodiment of the first aspect, the syngas oxidation reactor is selected as a countercurrent fluidized bed reactor.

[0032] 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.

[0033] According to a preferred embodiment of the first aspect, the second gas-solid separation device includes a cyclone separator and a riser, wherein the feed inlet of the cyclone separator is connected to the riser.

[0034] 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.

[0035] 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:

[0036] Methane and the first oxygen carrier enter the hydrocarbon conversion syngas reactor and undergo the first reaction in contact; wherein, based on the total mass of the first oxygen carrier being 100%, the first oxygen carrier is a mixture of 70-90% oxygen carrier A and 10-30% oxygen carrier B.

[0037] The product obtained from the first reaction enters the first gas-solid separation device for gas-solid separation, and the gas phase product is syngas and the solid phase product is the reduced first oxygen carrier.

[0038] Syngas and a second oxygen carrier enter a syngas oxidation reactor, where they come into contact and carry out a second reaction. The second oxygen carrier is a mixture of 10-20% oxygen carrier A and 80-90% oxygen carrier B, with the total mass of the second oxygen carrier being 100%.

[0039] The gaseous product obtained from the second reaction enters the second gas-solid separation device for gas-solid separation. The gaseous product obtained from the gas-solid separation is CO2, and the solid product is the reduced second oxygen carrier.

[0040] The solid product obtained from the second reaction and water vapor enter the hydrogen production reactor, where they come into contact to carry out the third reaction.

[0041] The product obtained from the third reaction enters the third gas-solid separation device for gas-solid separation, and the gas phase product is hydrogen and the solid phase product is a partially oxidized second oxygen carrier.

[0042] Among them, oxygen carrier A is selected with the chemical formula LaAl. 1 / 5 Co 1 / 5 Mn 1 / 5 Fe 1 / 5 Ni 1 / 5 O3 is used as an oxygen carrier, and oxygen carrier B is selected with the chemical formula LaAl. 1 / 4 Co 1 / 4 Mn 1 / 4 Fe 1 / 4 O3 oxygen carrier.

[0043] According to a preferred embodiment of the second aspect, the chemical looping hydrogen production method further includes:

[0044] The reduced first oxygen carrier obtained in the first gas-solid separation device and the first oxidizing gas enter the first oxygen carrier oxidation reactor, where they come into contact to carry out the fourth reaction.

[0045] The product obtained from the fourth 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.

[0046] The first oxygen carrier obtained from the fourth gas-solid separation unit is transported to the hydrocarbon conversion syngas reactor for recycling.

[0047] Furthermore, the reduced first oxygen carrier is treated using a third overflow tank before entering the first oxygen carrier oxidation reactor;

[0048] Furthermore, the first oxidizing gas is air;

[0049] Furthermore, the temperature of the fourth reaction is 900-1100℃; the pressure of the reduced first oxygen carrier is 0.1-0.3MPa;

[0050] Furthermore, the method also includes: the first oxygen carrier obtained by the fourth gas-solid separation device is treated by the fourth overflow tank before being transported to the hydrocarbon conversion syngas reactor for recycling.

[0051] According to a preferred embodiment of the second aspect, the chemical looping hydrogen production method further includes:

[0052] The reduced second oxygen carrier obtained from the second gas-solid separation device, the partially oxidized second oxygen carrier obtained from the third gas-solid separation device, and the second oxidizing gas enter the second oxygen carrier oxidation reactor, where they come into contact to carry out the fifth reaction.

[0053] The product obtained from the fifth reaction enters the fifth gas-solid separation device for gas-solid separation. The solid product obtained from the gas-solid separation is the second oxygen carrier.

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

[0055] Furthermore, the partially oxidized second oxygen carrier is treated using a fourth overflow tank before entering the second oxygen carrier oxidation reactor;

[0056] Furthermore, the second oxidizing gas is air;

[0057] Furthermore, the temperature of the fifth reaction is 900-1100℃; the pressure of the fifth reaction is 0.1-0.3MPa;

[0058] Furthermore, the second oxygen carrier obtained in the fifth gas-solid separation unit is treated in the sixth overflow tank before being transported to the syngas oxidation reactor for recycling.

[0059] 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.

[0060] According to a preferred embodiment of the second aspect, the ratio of methane to the first oxygen carrier is 1-3 mL: 1 g.

[0061] 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.

[0062] According to a preferred embodiment of the second aspect, the ratio of syngas to the second oxygen carrier is 1-3 mL: 1 g.

[0063] 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.

[0064] According to a preferred embodiment of the second aspect, the ratio of water vapor to the solid product obtained from the second reaction is 5-10 mL: 1 g.

[0065] According to a preferred embodiment of the second aspect, the gaseous products obtained in the syngas oxidation reactor are first treated using a first overflow tank before entering the second gas-solid separation device.

[0066] According to a preferred embodiment of the second aspect, the solid products obtained in the syngas oxidation reactor are first treated using a second overflow tank before entering the hydrogen production reactor.

[0067] The technical solution provided by this invention can simultaneously achieve continuous and efficient methane conversion, carbon dioxide capture, high hydrogen yield, and high hydrogen purity. Compared with the prior art, the technical solution provided by this invention has the following beneficial effects:

[0068] 1. The chemical chain hydrogen production technology solution provided by this invention can realize the continuous circulation operation of oxygen carrier, which is beneficial to the operation of large-scale industrial plants.

[0069] 2. The chemical chain hydrogen production technology provided by this invention can simultaneously achieve complete combustion of methane and efficient capture of carbon dioxide; at the same time, it can improve both the yield and purity of hydrogen.

[0070] 3. The chemical chain hydrogen production technology provided by this invention addresses the different requirements of the oxygen carrier's equilibrium oxygen partial pressure and surface active site structure for the processes of methane-to-syngas production and syngas-to-hydrogen production while simultaneously capturing CO2. It employs mixtures of oxygen carriers with different proportions and varying equilibrium oxygen partial pressures and surface active site structures to achieve complete methane conversion to syngas and syngas-to-hydrogen production while simultaneously capturing CO2. This is achieved using LaAl, a substrate with low equilibrium oxygen partial pressure, high methane activation capacity, and weak oxidizing ability. 1 / 5 Co 1 / 5 Mn 1 / 5 Fe 1 / 5 Ni1 / 5 O3 oxygen carrier and equilibrium oxygen partial pressure (pO2 = 10) -19 -10 -16 LaAl, after reduction, can be partially or completely oxidized by water vapor. 1 / 4 Co 1 / 4 Mn 1 / 4 Fe 1 / 4 With the help of O3 oxygen carrier, the process of producing hydrogen from methane through a chemical loop achieves high methane conversion rate, high CO2 capture rate, high hydrogen yield and high hydrogen purity.

[0071] 4. The technical solution provided by this invention uses a two-step method with a mixture of two specific oxygen carriers in different proportions to convert methane. This method can fully convert methane into CO2, improve the CO2 capture rate, reduce the reaction temperature, reduce carbon buildup on the oxygen carrier, and improve hydrogen purity. 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: a first oxygen carrier oxidation reactor 1, a hydrocarbon conversion syngas reactor 2, a syngas oxidation reactor 3, a hydrogen production reactor 4, a second oxygen carrier oxidation reactor 5, a first overflow tank 9, a second overflow tank 8, a third overflow tank 7, a fourth overflow tank 6, a fifth overflow tank 10, and a sixth overflow tank (…). Figure 1 (not shown in the image), first gas-solid separation device 12, second gas-solid separation device 13, third gas-solid separation device 14, fourth gas-solid separation device 11 and fifth gas-solid separation device (not shown in the image), Figure 1 (Not shown in the image).

[0077] The first gas-solid separation device 12 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 12 is located in the middle of the cyclone separator, the gas phase outlet of the first gas-solid separation device 12 is located at the top of the cyclone separator, and the solid phase outlet of the first gas-solid separation device 12 is located at the bottom of the riser. The fourth gas-solid separation device 11 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 11 is located at the bottom of the riser. In the middle of the air separator, the gas phase outlet of the fourth gas-solid separation device 11 is located at the top of the cyclone separator, and the solid phase outlet of the fourth gas-solid separation device 11 is located at the bottom of the riser. The product outlet of the hydrocarbon conversion syngas reactor 2 is connected to the feed inlet of the first gas-solid separation device 12, and the solid product outlet of the first gas-solid separation device 12 is connected to the solid feed inlet of the first oxygen carrier oxidation reactor 1. The third overflow tank 7 is located on the connecting pipeline between the solid product outlet of the first gas-solid separation device 12 and the solid feed inlet of the first oxygen carrier oxidation reactor 1, specifically located in the riser of the first gas-solid separation device 12. At the bottom of the pipe, the product outlet of the first oxygen carrier oxidation reactor 1 is connected to the feed inlet of the fourth gas-solid separation device 11, and the solid product outlet of the fourth gas-solid separation device 11 is connected to the solid feed inlet of the hydrocarbon conversion syngas reactor 2. The fourth overflow tank 6 is located on the connecting pipe between the solid product outlet of the fourth gas-solid separation device 11 and the solid feed inlet of the hydrocarbon conversion syngas reactor 2, specifically at the bottom of the riser of the fourth gas-solid separation device 11. The gas feed inlet of the hydrocarbon conversion syngas reactor 2 is used for hydrocarbon feed, and the gas feed inlet of the first oxygen carrier oxidation reactor 1... The feed inlet is used for feeding oxidizing gases, and both the third overflow tank 7 and the fourth overflow tank 6 are equipped with water vapor loosening air inlets; the first 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 hydrocarbon conversion syngas 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.

[0078] The second gas-solid separation device 13 includes a cyclone separator and a riser. The cyclone separator is located at the top of the riser, and the feed inlet 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 13 is located at the bottom of the riser. The gas phase outlet of the second gas-solid separation device 13 is located at the top of the cyclone separator, and the solid phase outlet of the second gas-solid separation device 13 is located in the middle of the cyclone separator. The third gas-solid separation device 14 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 14 is located in the middle of the cyclone separator, and the gas phase outlet of the third gas-solid separation device 14 is located at the top of the cyclone separator. The solid phase outlet of the third gas-solid separation device 14 is located in the middle of the cyclone separator. The fifth gas-solid separation device 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 fifth gas-solid separation device is located in the middle of the cyclone separator, the gas phase outlet of the fifth gas-solid separation device is located at the top of the cyclone separator, and the solid phase outlet of the fifth gas-solid separation device is located at the bottom of the riser. The gas phase product outlet of the first gas-solid separation device 12 is connected to the gas feed inlet of the syngas oxidation reactor 3, and the gas phase product outlet of the syngas oxidation reactor 3 is connected to the feed inlet of the second gas-solid separation device 13. The first overflow tank 9 is located on the connecting pipeline between the gas phase product outlet of the syngas oxidation reactor 3 and the feed inlet of the second gas-solid separation device 13. Specifically, a second overflow tank 8 is installed at the bottom of the riser of the second gas-solid separation device 13, connecting the solid product outlet of the syngas oxidation reactor 3 to the solid feed inlet of the hydrogen production reactor 4. The product outlet of the hydrogen production reactor 4 is connected to the feed inlet of the third gas-solid separation device 14. The solid product outlet of the second gas-solid separation device 13 is connected to the first solid feed inlet of the second oxygen carrier oxidation reactor 5, and the solid product outlet of the third gas-solid separation device 14 is connected to the second solid feed inlet of the second oxygen carrier oxidation reactor 5. A fifth overflow tank 10 is installed between the solid product outlet of the third gas-solid separation device 14 and the second oxygen carrier oxidation reactor 5. The connecting pipe between the solid feed inlets is specifically located at the bottom end of the riser of the third gas-solid separation device 14. The product outlet of the second oxygen carrier oxidation reactor 5 is connected to the feed inlet of the fifth gas-solid separation device. The gas phase product outlet of the fifth gas-solid separation device is connected to the solid feed inlet of the syngas oxidation reactor 3. The sixth overflow tank is located on the connecting pipe between the solid phase product outlet of the fifth gas-solid separation device and the solid feed inlet of the syngas oxidation reactor, specifically at the bottom end of the riser of the fifth gas-solid separation device. The second oxygen carrier oxidation reactor 5 is 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 a bubbling fluidized bed or a turbulent fluidized bed form, and the riser section adopts a fast fluidized bed form.The hydrogen production reactor 4 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 uses a bubbling fluidized bed or a turbulent fluidized bed, and the riser section uses a rapid fluidized bed. The syngas oxidation reactor 3 is a counter-current fluidized bed reactor. The gas inlet of the second oxygen carrier oxidation reactor 5 is used for feeding oxidizing gases, the gas phase product outlet of the second gas-solid separation device 13 is used for discharging carbon dioxide, the gas inlet of the hydrogen production reactor 4 is used for feeding water vapor, and the gas phase product outlet of the third gas-solid separation device 14 is used for discharging hydrogen. The first overflow tank 9, the fifth overflow tank 10, and the sixth overflow tank are all 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 2, where a first reaction takes place (including the reaction of methane and the first 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 first oxygen carrier, with a total mass of 100%, is a mixture of 90% oxygen carrier A and 10% oxygen carrier B. Oxygen carrier A is selected with the chemical formula LaAl. 1 / 5 Co 1 / 5 Mn 1 / 5 Fe 1 / 5 Ni 1 / 5 O3 is used as an oxygen carrier, and oxygen carrier B is selected with the chemical formula LaAl. 1 / 4 Co 1 / 4Mn 1 / 4 Fe 1 / 4 O3 oxygen carrier;

[0083] Among them, oxygen carrier A (LaAl) 1 / 5 Co 1 / 5 Mn 1 / 5 Fe 1 / 5 Ni 1 / 5 O3 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 LaAl 1 / 5 Co 1 / 5 Mn 1 / 5 Fe 1 / 5Ni 1 / 5The stoichiometric ratio of La, Al, Co, Mn, Fe, and Ni in O3 was determined by weighing out aqueous solutions of La(NO3)3·6H2O, Al(NO3)3·9H2O, Co(NO3)2·6H2O, Mn(NO3)2, Fe(NO3)3·9H2O, and Ni(NO3)2·6H2O, 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.

[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 atmosphere for 4 hours to obtain oxygen carrier A (LaAl). 1 / 5 Co 1 / 5 Mn 1 / 5 Fe 1 / 5 Ni 1 / 5 O3).

[0086] Among them, oxygen carrier B (LaAl) 1 / 4 Co 1 / 4 Mn 1 / 4 Fe 1 / 4 O3 can be prepared through the following process:

[0087] (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.

[0088] (2) The precursor solution was evaporated to a gel state under stirring; then aged in a 130℃ constant temperature drying oven for 12 hours to obtain precursor powder; the obtained precursor powder was calcined at 900℃ in air atmosphere for 4 hours to obtain oxygen carrier B (LaAl). 1 / 4 Co 1 / 4 Mn 1 / 4 Fe 1 / 4 O3).

[0089] The temperature of the first reaction is 1000℃; the pressure of the first reaction is atmospheric pressure.

[0090] The methane feed rate is 6000 mL / min, and the first oxygen carrier feed rate is 3000 g / min.

[0091] 2) The product obtained from the first reaction enters the first gas-solid separation device 12 for gas-solid separation, and the gas phase product is syngas and the solid phase product is the reduced first oxygen carrier.

[0092] 3) The reduced first oxygen carrier obtained in the first gas-solid separation device 12 is treated by the third overflow tank 7 and then enters the first oxygen carrier oxidation reactor 1 with the first oxidizing gas air. The fourth reaction is carried out in the first oxygen carrier oxidation reactor 1 (including the reaction of the reduced first oxygen carrier and 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 fourth reaction enters the fourth gas-solid separation device 11 for gas-solid separation, and 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 11 is treated by the fourth overflow tank 6 and then transported to the hydrocarbon conversion syngas reactor 2 for recycling;

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

[0094] The air feed rate is 12000 mL / min.

[0095] 4) Syngas and the second oxygen carrier enter the syngas oxidation reactor 3 and undergo a second reaction in countercurrent flow contact; wherein, based on the total mass of the second oxygen carrier being 100%, the second oxygen carrier is a mixture of 10% oxygen carrier A (the same as oxygen carrier A in step 1) and 90% oxygen carrier B (the same as oxygen carrier B in step 1);

[0096] The temperature of the second reaction is 900℃; the pressure of the second reaction is atmospheric pressure.

[0097] In step 1), the syngas obtained is approximately 18,000 mL / min, and the feed rate of the second oxygen carrier is 9,000 g / min.

[0098] 5) The gaseous product obtained from the second reaction is processed by the first overflow tank 9 and then enters the second gas-solid separation device 13 for gas-solid separation. The gaseous product obtained from the gas-solid separation is CO2, and the solid product is the reduced second oxygen carrier. The gaseous product CO2 is condensed and dehydrated for CO2 capture.

[0099] 6) The solid product obtained from the second reaction is treated by the second overflow tank 8 and then enters the hydrogen production reactor 4 with water vapor. The third reaction is carried out in the hydrogen production reactor 4 (including the reaction of the solid product obtained from the second reaction, i.e. the reduced second oxygen carrier, with water vapor 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).

[0100] The temperature of the third reaction is 900℃; the pressure of the third reaction is atmospheric pressure.

[0101] The steam feed rate is 30,000 mL / min, and the solid product obtained from the second reaction is fed into the hydrogen production reactor 4 at a rate of 9,000 g / min.

[0102] 7) The product obtained from the third reaction enters the third gas-solid separation device 14 for gas-solid separation, and the gas phase product is hydrogen and the solid phase product is a partially oxidized second oxygen carrier; the gas phase product hydrogen is collected after condensation.

[0103] 8) The reduced second oxygen carrier obtained in the second gas-solid separation device 13 and the partially oxidized second oxygen carrier obtained in the third gas-solid separation device 14 are treated by the fifth overflow tank 10 and then enter the second oxygen carrier oxidation reactor 5 with the second oxidizing gas air (including the partially oxidized second oxygen carrier obtained in the third gas-solid separation device 14 being treated by the fifth overflow tank 10 and then the reduced second oxygen carrier obtained in the second gas-solid separation device 13 reacting with air in the main reaction zone using a bubbling fluidized bed, and then entering the riser section using a rapid fluidized bed to continue the reaction), and the fifth reaction is carried out in the second oxygen carrier oxidation reactor 5; the product obtained from the fifth reaction enters the fifth gas-solid separation device for gas-solid separation, and the solid product obtained from the gas-solid separation is the second oxygen carrier; the second oxygen carrier obtained from the fifth gas-solid separation device is treated by the sixth overflow tank and then transported to the syngas oxidation reactor 3 for recycling;

[0104] The fifth reaction is carried out at a temperature of 1000℃ and a pressure of atmospheric pressure.

[0105] The air feed rate is 12000 mL / min.

[0106] Example 3

[0107] This embodiment provides a chemical chain hydrogen production method.

[0108] This method is carried out using the chemical chain hydrogen production system provided in Example 1, and the method includes:

[0109] 1) Methane and the first oxygen carrier enter the hydrocarbon conversion syngas reactor 2, where a first reaction takes place (including the reaction of methane and the first 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 first oxygen carrier, with a total mass of 100%, is a mixture of 90% oxygen carrier A and 10% oxygen carrier B. Oxygen carrier A is selected with the chemical formula LaAl. 1 / 5 Co 1 / 5 Mn 1 / 5 Fe 1 / 5 Ni 1 / 5 O3 is used as an oxygen carrier, and oxygen carrier B is selected with the chemical formula LaAl. 1 / 4 Co 1 / 4Mn 1 / 4 Fe 1 / 4 O3 oxygen carrier;

[0110] The temperature of the first reaction is 950℃; the pressure of the first reaction is atmospheric pressure.

[0111] The methane feed rate is 6000 mL / min, and the first oxygen carrier feed rate is 3000 g / min.

[0112] 2) The product obtained from the first reaction enters the first gas-solid separation device 12 for gas-solid separation, and the gas phase product is syngas and the solid phase product is the reduced first oxygen carrier.

[0113] 3) The reduced first oxygen carrier obtained in the first gas-solid separation device 12 is treated by the third overflow tank 7 and then enters the first oxygen carrier oxidation reactor 1 with the first oxidizing gas air. The fourth reaction is carried out in the first oxygen carrier oxidation reactor 1 (including the reaction of the reduced first oxygen carrier and 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 fourth reaction enters the fourth gas-solid separation device 11 for gas-solid separation, and 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 11 is treated by the fourth overflow tank 6 and then transported to the hydrocarbon conversion syngas reactor 2 for recycling;

[0114] The fourth reaction is carried out at a temperature of 1000℃ and a pressure of atmospheric pressure.

[0115] The air feed rate is 12000 mL / min.

[0116] 4) Syngas and the second oxygen carrier enter the syngas oxidation reactor 3 and undergo a second reaction in countercurrent flow contact; wherein, based on the total mass of the second oxygen carrier being 100%, the second oxygen carrier is a mixture of 10% oxygen carrier A (the same as oxygen carrier A in step 1) and 90% oxygen carrier B (the same as oxygen carrier B in step 1);

[0117] The temperature of the second reaction is 900℃; the pressure of the second reaction is atmospheric pressure.

[0118] In step 1), the syngas obtained is approximately 18,000 mL / min, and the feed rate of the second oxygen carrier is 9,000 g / min.

[0119] 5) The gaseous product obtained from the second reaction is processed by the first overflow tank 9 and then enters the second gas-solid separation device 13 for gas-solid separation. The gaseous product obtained from the gas-solid separation is CO2, and the solid product is the reduced second oxygen carrier. The gaseous product CO2 is condensed and dehydrated for CO2 capture.

[0120] 6) The solid product obtained from the second reaction is treated by the second overflow tank 8 and then enters the hydrogen production reactor 4 with water vapor. The third reaction is carried out in the hydrogen production reactor 4 (including the reaction of the solid product obtained from the second reaction, i.e. the reduced second oxygen carrier, with water vapor 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).

[0121] The temperature of the third reaction is 850℃; the pressure of the third reaction is atmospheric pressure.

[0122] The steam feed rate is 30,000 mL / min, and the solid product obtained from the second reaction is fed into the hydrogen production reactor 4 at a rate of 9,000 g / min.

[0123] 7) The product obtained from the third reaction enters the third gas-solid separation device 14 for gas-solid separation, and the gas phase product is hydrogen and the solid phase product is a partially oxidized second oxygen carrier; the gas phase product hydrogen is collected after condensation.

[0124] 8) The reduced second oxygen carrier obtained in the second gas-solid separation device 13 and the partially oxidized second oxygen carrier obtained in the third gas-solid separation device 14 are treated by the fifth overflow tank 10 and then enter the second oxygen carrier oxidation reactor 5 with the second oxidizing gas air (including the partially oxidized second oxygen carrier obtained in the third gas-solid separation device 14 being treated by the fifth overflow tank 10 and then the reduced second oxygen carrier obtained in the second gas-solid separation device 13 reacting with air in the main reaction zone using a bubbling fluidized bed, and then entering the riser section using a rapid fluidized bed to continue the reaction), and the fifth reaction is carried out in the second oxygen carrier oxidation reactor 5; the product obtained from the fifth reaction enters the fifth gas-solid separation device for gas-solid separation, and the solid product obtained from the gas-solid separation is the second oxygen carrier; the second oxygen carrier obtained from the fifth gas-solid separation device is treated by the sixth overflow tank and then transported to the syngas oxidation reactor 3 for recycling;

[0125] The fifth reaction is carried out at a temperature of 1000℃ and a pressure of atmospheric pressure.

[0126] The air feed rate is 12000 mL / min.

[0127] Example 4

[0128] This embodiment provides a chemical chain hydrogen production method.

[0129] This method is carried out using the chemical chain hydrogen production system provided in Example 1, and the method includes:

[0130] 1) Methane and the first oxygen carrier enter the hydrocarbon conversion syngas reactor 2, where a first reaction takes place (including the reaction of methane and the first 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 first oxygen carrier, with a total mass of 100%, is a mixture of 90% oxygen carrier A and 10% oxygen carrier B. Oxygen carrier A is selected with the chemical formula LaAl. 1 / 5 Co 1 / 5 Mn 1 / 5 Fe 1 / 5 Ni 1 / 5 O3 is used as an oxygen carrier, and oxygen carrier B is selected with the chemical formula LaAl. 1 / 4 Co 1 / 4Mn 1 / 4 Fe 1 / 4 O3 oxygen carrier;

[0131] The temperature of the first reaction is 1000℃; the pressure of the first reaction is atmospheric pressure.

[0132] The methane feed rate is 6500 mL / min, and the first oxygen carrier feed rate is 3000 g / min.

[0133] 2) The product obtained from the first reaction enters the first gas-solid separation device 12 for gas-solid separation, and the gas phase product is syngas and the solid phase product is the reduced first oxygen carrier.

[0134] 3) The reduced first oxygen carrier obtained in the first gas-solid separation device 12 is treated by the third overflow tank 7 and then enters the first oxygen carrier oxidation reactor 1 with the first oxidizing gas air. The fourth reaction is carried out in the first oxygen carrier oxidation reactor 1 (including the reaction of the reduced first oxygen carrier and 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 fourth reaction enters the fourth gas-solid separation device 11 for gas-solid separation, and 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 11 is treated by the fourth overflow tank 6 and then transported to the hydrocarbon conversion syngas reactor 2 for recycling;

[0135] The fourth reaction is carried out at a temperature of 1000℃ and a pressure of atmospheric pressure.

[0136] The air feed rate is 12000 mL / min.

[0137] 4) Syngas and the second oxygen carrier enter the syngas oxidation reactor 3 and undergo a second reaction in countercurrent flow contact; wherein, based on the total mass of the second oxygen carrier being 100%, the second oxygen carrier is a mixture of 10% oxygen carrier A (the same as oxygen carrier A in step 1) and 90% oxygen carrier B (the same as oxygen carrier B in step 1);

[0138] The temperature of the second reaction is 900℃; the pressure of the second reaction is atmospheric pressure.

[0139] In step 1), the syngas obtained is approximately 18,000 mL / min, and the feed rate of the second oxygen carrier is 9,000 g / min.

[0140] 5) The gaseous product obtained from the second reaction is processed by the first overflow tank 9 and then enters the second gas-solid separation device 13 for gas-solid separation. The gaseous product obtained from the gas-solid separation is CO2, and the solid product is the reduced second oxygen carrier. The gaseous product CO2 is condensed and dehydrated for CO2 capture.

[0141] 6) The solid product obtained from the second reaction is treated by the second overflow tank 8 and then enters the hydrogen production reactor 4 with water vapor. The third reaction is carried out in the hydrogen production reactor 4 (including the reaction of the solid product obtained from the second reaction, i.e. the reduced second oxygen carrier, with water vapor 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).

[0142] The temperature of the third reaction is 900℃; the pressure of the third reaction is atmospheric pressure.

[0143] The steam feed rate is 35,000 mL / min, and the solid product obtained from the second reaction is fed into the hydrogen production reactor 4 at a rate of 9,000 g / min.

[0144] 7) The product obtained from the third reaction enters the third gas-solid separation device 14 for gas-solid separation, and the gas phase product is hydrogen and the solid phase product is a partially oxidized second oxygen carrier; the gas phase product hydrogen is collected after condensation.

[0145] 8) The reduced second oxygen carrier obtained in the second gas-solid separation device 13 and the partially oxidized second oxygen carrier obtained in the third gas-solid separation device 14 are treated by the fifth overflow tank 10 and then enter the second oxygen carrier oxidation reactor 5 with the second oxidizing gas air (including the partially oxidized second oxygen carrier obtained in the third gas-solid separation device 14 being treated by the fifth overflow tank 10 and then the reduced second oxygen carrier obtained in the second gas-solid separation device 13 reacting with air in the main reaction zone using a bubbling fluidized bed, and then entering the riser section using a rapid fluidized bed to continue the reaction), and the fifth reaction is carried out in the second oxygen carrier oxidation reactor 5; the product obtained from the fifth reaction enters the fifth gas-solid separation device for gas-solid separation, and the solid product obtained from the gas-solid separation is the second oxygen carrier; the second oxygen carrier obtained from the fifth gas-solid separation device is treated by the sixth overflow tank and then transported to the syngas oxidation reactor 3 for recycling;

[0146] The fifth reaction is carried out at a temperature of 1000℃ and a pressure of atmospheric pressure.

[0147] The air feed rate is 12000 mL / min.

[0148] Comparative Example 1

[0149] This comparative example provides a chemical chain hydrogen production method.

[0150] 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 first oxygen carrier oxidation reactor 1, the hydrocarbon conversion syngas reactor 2, the third overflow tank 7, the fourth overflow tank 6, the first gas-solid separation device 12, and the fourth gas-solid separation device 11.

[0151] This method differs from the chemical chain hydrogen production method provided in Example 2 by omitting steps 1)-3), and in step 4), the gas entering the syngas oxidation reactor 3 is methane instead of syngas, and the methane feed rate is the same as that in Example 2.

[0152] Comparative Example 2

[0153] This example provides a chemical chain hydrogen production method, wherein the difference between this method and Example 2 is that both the first oxygen carrier and the second oxygen carrier are the same as the first oxygen carrier used in Example 2.

[0154] Comparative Example 3

[0155] This comparative example provides a chemical chain hydrogen production method, wherein the difference between this method and Example 2 is that both the first oxygen carrier and the second oxygen carrier are the second oxygen carrier used in Example 2.

[0156] The CH4 conversion, CO2 selectivity, H2 yield, and H2 purity of each embodiment and comparative example are shown in Table 1 below.

[0157] Table 1

[0158] Serial Number <![CDATA[CH4 conversion rate (%)]]> <![CDATA[CO2 selectivity (%)]]> <![CDATA[H2 production rate mmol / g]]> <![CDATA[H2 purity (%)]]> Example 2 68 95 2.7 99.5 Example 3 63 92 2.0 95.2 Example 4 62 91 2.1 94.8 Comparative Example 1 56 87 1.2 89.7 Comparative Example 2 58 90 1.7 93.1 Comparative Example 3 57 86 1.8 93.9

[0159] 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 gas-solid separation unit, a syngas oxidation reactor, a second gas-solid separation unit, a hydrogen production reactor, and a third gas-solid separation unit; The product outlet of the hydrocarbon conversion syngas reactor is connected to the inlet of the first gas-solid separation device. The gas phase product outlet of the first gas-solid separation device is connected to the gas inlet of the syngas oxidation reactor. The gas phase product outlet of the syngas oxidation reactor is connected to the inlet of the second gas-solid separation device. The solid phase product outlet of the syngas oxidation reactor is connected to the solid inlet of the hydrogen production reactor. The product outlet of the hydrogen production reactor is connected to the 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 feedlet is used for oxygen carrier feed; the solid feedlet 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 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.

2. The system according to claim 1, wherein, The chemical looping reaction hydrogen production system also includes a first 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 first oxygen carrier oxidation reactor, the product outlet of the first 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 first oxygen carrier oxidation reactor is used for feeding oxidizing gases.

3. The system according to claim 2, wherein, The first oxygen carrier oxidation 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, 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; and / or 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.

4. The system according to claim 1, wherein, The chemical looping reaction hydrogen production system also includes a second oxygen carrier oxidation reactor and a fifth gas-solid separation unit; The solid product outlet of the second gas-solid separation unit is connected to the solid feed inlet of the second oxygen carrier oxidation reactor. The solid product outlet of the third gas-solid separation device is connected to the solid feed inlet of the second oxygen carrier oxidation reactor, the product outlet of the second oxygen carrier oxidation reactor is connected to the feed inlet of the fifth gas-solid separation device, and the gaseous product outlet of the fifth gas-solid separation device is connected to the solid feed inlet of the syngas oxidation reactor. The gas inlet of the second oxygen carrier oxidation reactor is used for feeding oxidizing gases.

5. The system according to claim 4, wherein, The second oxygen carrier oxidation 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 fifth 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.

6. The system according to claim 1, wherein, The hydrocarbon conversion syngas 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. The main reaction zone employs a bubbling fluidized bed or a turbulent fluidized bed, while the riser section employs a rapid fluidized bed; and / or The 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. The main reaction zone employs a bubbling fluidized bed or a turbulent fluidized bed configuration, while the riser section employs a rapid fluidized bed configuration; and / or The syngas oxidation reactor is a countercurrent fluidized bed reactor.

7. 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 feed inlet 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.

8. 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 1-7, the method comprising: Methane and the first oxygen carrier enter the hydrocarbon conversion syngas reactor and undergo the first reaction in contact; wherein, based on the total mass of the first oxygen carrier being 100%, the first oxygen carrier is a mixture of 70-90% oxygen carrier A and 10-30% oxygen carrier B. The product obtained from the first reaction enters the first gas-solid separation device for gas-solid separation, and the gas phase product is syngas and the solid phase product is the reduced first oxygen carrier. Syngas and a second oxygen carrier enter a syngas oxidation reactor, where they come into contact and carry out a second reaction. The second oxygen carrier is a mixture of 10-20% oxygen carrier A and 80-90% oxygen carrier B, with the total mass of the second oxygen carrier being 100%. The gaseous product obtained from the second reaction enters the second gas-solid separation device for gas-solid separation. The gaseous product obtained from the gas-solid separation is CO2, and the solid product is the reduced second oxygen carrier. The solid product obtained from the second reaction and water vapor enter the hydrogen production reactor, where they come into contact to carry out the third reaction. The product obtained from the third reaction enters the third gas-solid separation device for gas-solid separation, and the gas phase product is hydrogen and the solid phase product is a partially oxidized second oxygen carrier. Among them, oxygen carrier A is selected with the chemical formula LaAl. 1 / 5 Co 1 / 5 Mn 1 / 5 Fe 1 / 5 Ni 1 / 5 O3 is used as an oxygen carrier, and oxygen carrier B is selected with the chemical formula LaAl. 1 / 4 Co 1 / 4 Mn 1 / 4 Fe 1 / 4 O3 oxygen carrier.

9. The method according to claim 8, wherein, Chemical chain hydrogen production methods also include: The reduced first oxygen carrier obtained in the first gas-solid separation device and the first oxidizing gas enter the first oxygen carrier oxidation reactor, where they come into contact to carry out the fourth reaction. The product obtained from the fourth 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 first oxygen carrier obtained from the fourth gas-solid separation unit is transported to the hydrocarbon conversion syngas reactor for recycling. Preferably, the first oxidizing gas is air; Preferably, the temperature of the fourth reaction is 900-1100℃; the pressure of the fourth reaction is 0.1-0.3MPa.

10. The method according to claim 8, wherein, Chemical chain hydrogen production methods also include: The reduced second oxygen carrier obtained from the second gas-solid separation device, the partially oxidized second oxygen carrier obtained from the third gas-solid separation device, and the second oxidizing gas enter the second oxygen carrier oxidation reactor, where they come into contact to carry out the fifth reaction. The product obtained from the fifth reaction enters the fifth gas-solid separation device for gas-solid separation. The solid product obtained from the gas-solid separation is the second oxygen carrier. The second oxygen carrier obtained from the fifth gas-solid separation unit is transported to the syngas oxidation reactor for recycling. Preferably, the second oxidizing gas is air; Preferably, the temperature of the fifth reaction is 900-1100℃; the pressure of the fifth reaction is 0.1-0.3MPa.

11. The method according to claim 8, wherein, The temperature of the first reaction is 900-1100℃; the pressure of the first reaction is 0.1-0.3MPa.

12. The method according to claim 8, wherein, The ratio of methane to the first oxygen carrier is 1-3 mL: 1 g.

13. The method according to claim 8, wherein, The temperature of the second reaction is 800-900℃; the pressure of the second reaction is 0.1-0.3MPa.

14. The method according to claim 8, wherein, The ratio of synthesis gas to the second oxygen carrier is 1-3 mL: 1 g.

15. The method according to claim 8, wherein, The temperature of the third reaction is 850-950℃; the pressure of the third reaction is 0.1-0.3MPa.

16. The method according to claim 8, wherein, The ratio of water vapor to the solid product obtained from the second reaction is 5-10 mL: 1 g.

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