Method and apparatus for high temperature electrolysis for syngas production

Abstract

The application discloses a method and device for preparing synthesis gas by high-temperature electrolysis, and the method comprises the following steps: raw gas enters an electrolytic cell from an anode inlet, anode tail gas directly enters a cathode of the electrolytic cell, and finally, the anode tail gas exits the electrolytic cell from a cathode outlet; the raw gas comprises hydrocarbon fuel, water vapor and / or carbon dioxide, and the hydrocarbon fuel comprises methane, ethane, propane, methanol, ethanol and / or biomass gasification gas; the water vapor and / or carbon dioxide in the raw gas undergoes an electrolytic reduction reaction in the cathode to generate hydrogen and / or carbon monoxide, and the hydrocarbon fuel in the raw gas undergoes a partial oxidation reaction in the anode to generate hydrogen and carbon monoxide. The application has the advantages that the design of the gas inlet and outlet path and the management of the gas composition of the device for preparing synthesis gas by hydrocarbon fuel assisted solid oxide electrolysis are simplified, the carbon deposition resistance of the anode is enhanced, and the stability and reliability of the device operation are improved.

Description

Technical Field

[0001] This invention relates to a method and apparatus for preparing syngas, and more particularly to a method and apparatus for preparing syngas by high-temperature electrolysis. Background Technology

[0002] Syngas is a mixed gas primarily composed of H2 and CO. It is an important raw material or intermediate in the petrochemical industry, widely used in the synthesis of bulk chemical products such as ammonia, olefins, and methanol. Coal gasification and natural gas conversion are two main traditional methods for producing syngas. The former uses oxygen or steam as gasifying agents to convert the combustible components in coal or coke into gas at high temperatures; its effective components include CO, H2, CO2, and CH4. The latter, based on steam reforming, carbon dioxide reforming, partial oxidative reforming, or a combination of these methods, converts natural gas into syngas with different H2 / CO molar ratios. These thermochemical technologies are mature and have high production capacity, but they consume large amounts of non-renewable fossil fuels and require harsh conditions such as high temperature and high pressure, leading to high energy consumption, resource waste, and environmental pollution.

[0003] Solid oxide electrolyzers (SOECs) are all-solid-state electrochemical devices based on ceramic electrolyte diaphragms. Operating at temperatures typically between 400-1000℃, they can utilize renewable electricity to electrolyze H2O into H2 and O2, or CO2 into CO and O2, thus converting surplus electrical energy into fuel chemical energy. SOECs can also simultaneously co-electrolyze H2O / CO2 to generate syngas and O2, making them one of the important emerging alternative technologies for the sustainable production of syngas.

[0004] In existing technologies, Energy & Fuels 2009, 23, 3089–3096 uses a traditional flat-plate SOEC, CN116200755A uses a hollow flat-tube SOEC, and CN103613066A uses a microtube SOEC. In these technologies, H2O / CO2 is co-electrolyzed into syngas at the cathode, while O2 is simultaneously generated at the anode. International Journal of Hydrogen Energy 2021, 46, 20305-20312 introduces CH4 fuel into the SOEC anode, CN107180985A introduces low-concentration coalbed methane containing gases such as CH4, N2, and CO2 into the SOEC anode, and CN107868962A introduces a mixture of carbon powder, catalyst, and molten salt into the SOEC anode. This allows the oxygen ions generated by co-electrolysis and transported to the anode side to react with hydrocarbon fuels or solid carbon present on the anode side to generate syngas or carbon monoxide, thereby reducing the energy consumption of the electrolysis process.

[0005] However, these hydrocarbon fuel or solid carbon fuel-assisted SOEC electrolysis technologies have the following problems in practical applications: First, the input and output gases of the cathode and anode are independent of each other, resulting in a complex "two-inlet, two-outlet" structural design; second, the high-purity or high-concentration hydrocarbon fuel (such as CH4) input at the anode inlet is prone to cracking and carbon deposition at high temperatures, leading to anode structural damage and performance degradation, or even complete failure; third, while inputting H2O and / or CO2 at the cathode inlet, a certain amount of H2 or CO is often required simultaneously as a safety gas to prevent the cathode from failing due to oxidation reactions (such as Ni being oxidized to NiO) in high-concentration H2O / CO2. Summary of the Invention

[0006] Purpose of the Invention: This invention aims to provide a method and apparatus for producing syngas via high-temperature electrolysis of SOEC using a "one-inlet, one-outlet" system, solving problems such as complex inlet and outlet gas path design, gas composition management, and anode carbon buildup faced by hydrocarbon fuel-assisted solid oxide electrolyzers. Technical Solution: This invention provides a method for producing syngas using a solid oxide electrolyzer. The method includes: a raw material gas entering the electrolyzer from the anode inlet; the anode tail gas directly entering the cathode of the electrolyzer; and finally exiting the electrolyzer from the cathode outlet. The raw material gas includes hydrocarbon fuels, water vapor, and / or carbon dioxide. The hydrocarbon fuels include, but are not limited to, methane, ethane, propane, methanol, ethanol, and biomass gasification gas. The water vapor and / or carbon dioxide in the raw material gas undergo an electrolytic reduction reaction at the cathode to generate hydrogen and / or carbon monoxide. The hydrocarbon fuels in the raw material gas undergo a partial oxidation reaction at the anode to generate hydrogen and carbon monoxide.

[0007] The solid oxide electrolytic reactor for high-temperature electrolytic synthesis of syngas according to the present invention includes an anode end plate, an intermediate plate assembly and a cathode end plate. The intermediate plate assembly includes several repeating units, and each repeating unit is connected to the others by a connecting plate.

[0008] The repeating unit includes an anode seal, an anode current collector, an electrolytic cell, a cathode current collector, a middle frame, and a cathode seal, which are sequentially packaged. The anode seal, the middle frame, and the cathode seal are all hollow frames, and the seals seal the electrolytic cell, the current collector, and the middle frame onto the connecting plate.

[0009] The anode end plate, the repeating unit, and the connecting plate each have at least one air inlet and one air outlet on one side, the repeating unit has at least one opening on the other side, and the cathode end plate has no opening.

[0010] In the electrolytic cell, the feed gas enters the cell through the anode inlet, and the tail gas from the anode directly enters the cathode, finally exiting the cell through the cathode outlet. The feed gas consists of hydrocarbon fuels, water vapor, carbon dioxide, etc., and the hydrocarbon fuels include, but are not limited to, methane, ethane, propane, methanol, ethanol, and biomass gasification gas. The hydrocarbon fuels in the feed gas undergo partial oxidation at the anode to generate syngas, while the water vapor and / or carbon dioxide in the feed gas undergo electrolytic reduction at the cathode to generate hydrogen and / or carbon monoxide.

[0011] Furthermore, the electrolytic cell includes a cathode, an anode, and an electrolyte, wherein the cathode, the electrolyte, and the anode are subjected to processes such as high-temperature sintering to form a tight interfacial bond.

[0012] Furthermore, the electrolyte is a ceramic material with oxygen ion conductivity, including but not limited to yttrium-stabilized zirconium oxide, scandium oxide-stabilized zirconium oxide, cerium oxide doped, strontium magnesium doped lanthanum gallate, barium zirconate doped, and barium cerate doped.

[0013] Furthermore, both the cathode and the anode are composite ceramics composed of an electronically conductive phase and an oxygen ion-conducting phase, wherein the volume fraction of the electronically conductive phase in the solid phase is not less than 40%.

[0014] Furthermore, the electronically conductive phases in the cathode and anode are metals, alloys, conductive ceramics, or composites thereof, including but not limited to Ni, Cu, 430L, and (La). 1-x Sr x (Cr) 1-y Fe y )O 3-δ 、(La 1-x Sr x (Cr) 1-y Mn y )O 3-δ La 2- x Sr x Fe 2-y-z Ni y Mo z O 6-δ 430L-(La 1-x Sr x (Cr) 1-y Fe y )O 3-δ wait.

[0015] Furthermore, the oxygen ion conducting phases in the cathode and anode are oxides with oxygen ion conduction capabilities, including but not limited to yttrium-stabilized zirconium oxide, scandium oxide-stabilized zirconium oxide, cerium oxide doped, strontium magnesium doped lanthanum gallate, barium zirconate doped, and barium cerate doped.

[0016] Furthermore, the electrolyte is dense, with a thickness ranging from 1 to 1000 micrometers, preferably from 10 to 30 micrometers.

[0017] Furthermore, both the cathode and anode are porous, with a porosity ranging from 5% to 95%, preferably from 30% to 50%.

[0018] Furthermore, the thickness of the cathode and anode ranges from 0.05 to 1.5 mm, preferably from 0.1 to 0.5 mm.

[0019] Furthermore, the chemical composition, porosity, and thickness of the cathode and the anode may be the same or different.

[0020] Furthermore, the operating temperature range of the solid oxide electrolytic cell is 400-1000℃, preferably 500-750℃.

[0021] Furthermore, the operating voltage between the cathode and anode of the solid oxide electrolytic cell is 0.1-2.0V, preferably in the range of 0.3-1.3V.

[0022] Preferably, the inner wall of the cathode pore is coated with a nano-catalyst material, including but not limited to Ni, Fe, Co, FeNi3, and Ce. 1-x Sm x O 2-δ Ce 1-x Gd x O 2-δ 、(La 1-x Sr x (Co) 1-y Fe y )O 3-δ 、(Ba 1-x Sr x (Co) 1-y Fe y )O 3-δ 、(Sm 1- x Sr x CoO 3-δ SmBaCo2O 5+δ LaBa 0.5 Sr 0.5 Co2O 5+δ 、SmBa 0.5 Sr 0.5 Co2O 5+δ 、BaGd 0.8 La 0.2 Co2O 6-δ La 2- x Srx Fe 2-y-z Ni y Mo z O 6-δ wait.

[0023] Preferably, the inner wall of the pores of the anode is coated with a nano-catalyst material, including but not limited to Ni, Fe, Co, FeNi3, and Ce. 1-x Sm x O 2-δ Ce 1-x Gd x O 2-δ 、(La 1-x Sr x (Co) 1-y Fe y )O 3-δ 、(Ba 1-x Sr x (Co) 1-y Fe y )O 3-δ 、(Sm 1- x Sr x CoO 3-δ SmBaCo2O 5+δ LaBa 0.5 Sr 0.5 Co2O 5+δ 、SmBa 0.5 Sr 0.5 Co2O 5+δ 、BaGd 0.8 La 0.2 Co2O 6-δ La 2- x Sr x Fe 2-y-z Ni y Mo z O 6-δ wait.

[0024] Furthermore, the anode end plate is the top surface of the electrolytic stack, and the cathode end plate is the bottom surface of the electrolytic stack. The anode seal, anode current collector, middle frame, electrolytic cell, cathode seal, cathode current collector, and connecting plate constitute a repeating unit of the electrolytic stack.

[0025] Furthermore, the anode seal, the middle frame, and the cathode seal are all hollow frames. The seals enclose the electrolytic cell and the middle frame on the connecting plate. The top surface of the middle frame is sealed to the bottom surface of the connecting plate or the bottom surface of the anode end plate in the adjacent repeating unit through the anode seal, forming an anode chamber; the bottom surface of the middle frame is sealed to the top surface of the connecting plate or the top surface of the cathode end plate through the cathode seal, forming a cathode chamber.

[0026] Furthermore, the anode current collector fills the anode chamber, and the top surface of the anode current collector is in close contact with the bottom surface of the connecting plate or the bottom surface of the anode end plate in the adjacent repeating unit, and the bottom surface of the anode current collector is in close contact with the anode of the electrolytic cell; the cathode current collector fills the cathode chamber, and the top surface of the cathode current collector is in close contact with the cathode of the electrolytic cell, and the bottom surface of the cathode current collector is in close contact with the top surface of the connecting plate or the top surface of the cathode end plate.

[0027] Furthermore, the right side of the anode end plate is provided with the raw material gas inlet and the product gas outlet of the electrolytic reactor; the right side of the anode seal, the middle frame, the cathode seal, and the connecting plate are provided with suitable openings to ensure that the anode chamber in different repeating units is connected to the raw material gas inlet, and the cathode chamber in different repeating units is connected to the product gas outlet.

[0028] Furthermore, suitable openings are provided on the left side of the middle frame, the middle frame seal, and the middle frame bottom plate to ensure that the anode chamber and the cathode chamber of the electrolytic cell are connected, so that the tail gas of the anode can directly enter the cathode chamber of the electrolytic cell.

[0029] Furthermore, the anode end plate, anode seal, middle frame, cathode seal, connecting plate, and cathode end plate are all dense.

[0030] Furthermore, the anode plate, middle frame, connecting plate, and cathode plate are high-temperature alloys or conductive oxides with thermal expansion coefficients close to those of the electrolyte, including but not limited to 430L, 441, 446, Crofer, and (La) 1-x Sr x TiO 3–δ La 2-x Sr x Fe 2-y-z Ni y Mo z O 6-δ wait.

[0031] Furthermore, the surfaces of the anode plate, connecting plate, and cathode plate are covered with a conductive protective coating, including but not limited to Ni, Fe, Co, FeNi3, (La)1-x Sr x (Cr) 1-y Fe y )O 3–δ 、(La 1-x Sr x (Cr) 1-y Mn y )O 3–δ 、(La 1-x Sr x TiO 3–δ La 2-x Sr x Fe 2-y-z Ni y Mo z O 6-δ wait.

[0032] Furthermore, the anode current collector and cathode current collector are metals, alloys, conductive oxides, or composites thereof with high porosity and good electronic conductivity, including but not limited to nickel foam, nickel felt, nickel mesh, copper foam, copper felt, copper mesh, stainless steel mesh, and porous (La) materials. 1-x Sr x TiO 3–δ Porous La 2-x Sr x Fe 2-y-z Ni y Mo z O 6-δ wait.

[0033] Furthermore, the anode seal and cathode seal are high-temperature sealing materials with high resistivity, including but not limited to glass, mica, or vermiculite.

[0034] Furthermore, the present invention provides a high-temperature and high-pressure electrolytic synthesis gas preparation apparatus, comprising a high-pressure vessel and the aforementioned high-temperature electrolytic synthesis gas preparation solid oxide electrolytic reactor, wherein the high-temperature electrolytic synthesis gas preparation solid oxide electrolytic reactor is placed in the cavity of the high-pressure vessel, and the cavity of the high-pressure vessel is connected to the cathode chamber and the anode chamber of the solid oxide electrolytic reactor.

[0035] Furthermore, the present invention provides hydrocarbon fuel synthesis equipment, including the aforementioned high-temperature and high-pressure electrolytic synthesis gas preparation device, a fuel high-pressure synthesis module, a thermal management module, and an intelligent control module. The high-pressure synthesis gas generated by the high-temperature and high-pressure electrolytic synthesis gas preparation device directly enters the fuel high-pressure synthesis module and is converted into hydrocarbon fuel. The thermal management module consists of one or more components selected from a steam generator, a heat exchanger, and an electric heater, and is used to preheat the feedstock gas and recover the waste heat of the process gas and product gas. The hydrocarbon fuel includes, but is not limited to, methanol, ethanol, gasoline, diesel, and sustainable aviation kerosene.

[0036] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: (1) It simplifies the design of the gas inlet and outlet paths for producing syngas in hydrocarbon fuel-assisted solid oxide electrolysis reactors, and manages the gas inlet components, realizing "one gas inlet and one gas outlet", which enhances the anti-coking performance of the anode and improves the stability and reliability of the device operation; (2) Since the cavity of the high-pressure vessel is connected to the cathode chamber and the anode chamber, it can not only realize the high-pressure operation of SOEC, but also directly connect to the fuel high-pressure synthesis module, simplifying the system design and improving the system energy efficiency. Attached Figure Description

[0037] Figure 1 This is a schematic diagram illustrating the principle of the apparatus for producing syngas according to the present invention.

[0038] Figure 2 This is a schematic diagram of the packaging structure of the device described in this invention;

[0039] Figure 3 This is a schematic diagram of the encapsulation structure of a repeating unit in an electrolytic reactor. Detailed Implementation

[0040] The technical solution of the present invention will be further described below with reference to the accompanying drawings.

[0041] Figure 1-3 The accompanying figure labels are as follows:

[0042] 100 Electrolytic cell 8 Anode plate 1 anode 9 Anode seals 2 Electrolytes 10 Anode current collector 3 cathode 11 Mid-frame 4 Electron-conducting phase 12 Cathode seal 5 oxygen ion conductive phase 13 Cathode current collector 6 Anode nanocatalyst materials 14 Connecting plate 7 Cathode nanocatalyst materials 15 negative extreme plate 200 raw material gas 16 Anode chamber 300 Product gas 17 Cathode chamber 400 Electrolytic reactor 18 Raw material gas inlet 500 Repeating unit 19 Product gas outlet

[0043] Example 1

[0044] like Figure 2 As shown, the solid oxide electrolytic stack 400 includes an anode end plate 8, an anode seal 9, an anode current collector 10, an electrolytic cell 100, a middle frame 11, a cathode current collector 13, a cathode seal 12, a connecting plate 14, and a cathode end plate 15.

[0045] The electrolytic cell 100 includes an anode 1, an electrolyte 2, and a cathode 3, which are sintered from top to bottom. Figure 1 The raw material gas 200 enters the electrolytic cell 100 from the inlet of the anode 1, the tail gas of the anode 1 directly enters the cathode 3 of the electrolytic cell 100, and the product gas 300 of the cathode 3 leaves the electrolytic cell 100 from the outlet of the cathode 3.

[0046] The anode end plate 8 is the top surface of the electrolytic stack 400, and the cathode end plate 15 is the bottom surface of the electrolytic stack 400. The cathode end plate 15 has no openings. The anode seal 9, anode current collector 10, electrolytic cell 100, cathode seal 12, middle frame 11, and cathode current collector 13 constitute a repeating unit 500 of the electrolytic stack 400. Figure 3 Each repeating unit 500 is connected to the other via a connecting plate 14.

[0047] The anode seal 9, the middle frame 11, and the cathode seal 12 are all hollow frames, and the seals seal the electrolytic cell 100 and the middle frame 11 onto the connecting plate 14.

[0048] The top surface of the middle frame 11 is sealed together with the bottom surface of the connecting plate 14 or the bottom surface of the anode end plate 8 in the adjacent repeating unit 500 through the anode sealing member 9, forming an anode chamber 16; the bottom surface of the middle frame 11 is sealed together with the top surface of the connecting plate 14 or the top surface of the cathode end plate 15 through the cathode sealing member 12, forming a cathode chamber 17.

[0049] The anode current collector 10 fills the anode chamber 16, and the top surface of the anode current collector 10 is in close contact with the bottom surface of the connecting plate 14 or the bottom surface of the anode end plate 8 in the adjacent repeating unit 500. The bottom surface of the anode current collector 10 is in close contact with the anode 1 of the electrolytic cell 100. The cathode current collector 13 fills the cathode chamber 17, and the top surface of the cathode current collector 13 is in close contact with the cathode 3 of the electrolytic cell 100. The bottom surface of the cathode current collector 13 is in close contact with the top surface of the connecting plate 14 or the top surface of the cathode end plate 15.

[0050] like Figure 2 As shown, the right side of the anode end plate 8 is provided with the raw material gas inlet 18 and the product gas outlet 19 of the electrolytic stack 400; the right side of the anode seal 9, the middle frame 11, the cathode seal 12, and the connecting plate 14 are provided with suitable openings to ensure that the anode chamber 16 in different repeating units 500 is connected to the raw material gas inlet 18, and the cathode chamber 17 in different repeating units 500 is connected to the product gas outlet 19.

[0051] The left side of the middle frame 11 is provided with a suitable opening to ensure that the anode chamber 16 of the electrolytic cell 100 is connected to the cathode chamber 17, so that the tail gas of the anode 1 can directly enter the cathode chamber 17 of the electrolytic cell 100.

[0052] The anode end plate 8, anode seal 9, middle frame 11, cathode seal 12, connecting plate 14, and cathode end plate 5 are all dense.

[0053] The anode end plate 8, anode current collector 10, anode 1 and cathode 3 of the electrolytic cell 100, cathode current collector 13, connecting plate 14, and cathode end plate 15 all possess high electronic conductivity, while the electrolyte 2 of the electrolytic cell 100 possesses high oxygen ion conductivity. The tight interfacial contact between adjacent components minimizes interfacial contact resistance and promotes rapid electron transport. Both the anode current collector 10 and cathode current collector 13 have high porosity, which promotes rapid gas transport and uniform distribution within the anode chamber 18 and cathode chamber 19, respectively, thereby increasing the electrode reaction rate.

[0054] Both the anode seal 9 and the cathode seal 12 have high resistance, which prevents short circuits between the anode 1 and the cathode 3 of the electrolytic cell 100, and also prevents short circuits between adjacent repeating units 500.

[0055] The anode plate 8, middle frame 11, connecting plate 14, and cathode plate 15 are made of high-temperature alloy 446, whose coefficient of thermal expansion is close to that of electrolyte 2 in electrolytic cell 100. The surfaces of the anode plate 8, connecting plate 14, and cathode plate 15 are covered with a conductive protective coating of FeNi3 alloy.

[0056] The anode current collector 10 and the cathode current collector 13 are nickel foam metals with high porosity and good electronic conductivity.

[0057] The anode seal 9 and the cathode seal 13 are high-temperature sealing glasses with high resistivity.

[0058] The inner wall of the pores of the anode 1 is covered with an anode nanocatalyst material 6, wherein the nanocatalyst material 6 is Ce. 0.8 Gd 0.2 O2. The inner wall of the cathode 3 is covered with a nanocatalyst material 7, which is La. 0.5 Sr 1.5 Fe 1.5 Ni 0.1 Mo 0.4 O6.

[0059] Example 2

[0060] Based on the apparatus described in Example 1, a raw material gas 200 is introduced at the raw material gas inlet 18. The raw material gas 200 consists of CH4, H2O, and CO2, with a volume ratio of CH4:H2O:CO2 = 3:2:1. A voltage of 0.5V is applied between the anode 1 and the cathode 3.

[0061] When the raw material gas 200 passes through anode 1, CH4 reacts with O2 generated by cathode electrolysis and transported through electrolyte 2. 2- A reaction occurs, producing H2 and CO. The anodic reaction is...

[0062] After the tail gas from the anode enters cathode 3, the H2O and CO2 in the mixed gas will undergo a co-electrolysis reaction. The cathode reaction is 2H2O + CO2 + 6e - →2H₂ + CO + 3O 2- .

[0063] The overall reaction in electrolytic cell 100 is 3CH4 + 2H2O + CO2 → 8H2 + 4CO. It can be seen that the product gas 300 at cathode 3 is synthesis gas, with a volume ratio of H2 to CO of 2. The product gas is collected from product gas outlet 19.

[0064] Example 3

[0065] Based on the apparatus described in Example 1, a raw material gas 200 is introduced at the raw material gas inlet 18. The raw material gas 200 consists of ethanol and water vapor, with a volume ratio of C2H6O:H2O = 1:1. A voltage of 0.4V is applied between the anode 1 and the cathode 3.

[0066] When the raw material gas 200 passes through anode 1, C2H6O reacts with the O2 generated by cathode electrolysis and is transferred through electrolyte 2. 2- A reaction occurs, producing H2 and CO. The anodic reaction is...

[0067] After the tail gas from the anode enters cathode 3, the H2O in the mixed gas will undergo an electrolysis reaction, with the cathode reaction being H2O + 2e-. - →H2+O 2- .

[0068] The overall reaction in electrolytic cell 100 is C2H6O+H2O→4H2+2CO. It can be seen that the product gas 300 of cathode 3 is synthesis gas, with a volume ratio of H2 to CO of 2. The product gas is collected from product gas outlet 19.

[0069] Example 4

[0070] Based on the apparatus described in Example 1, a raw material gas 200 is introduced at the raw material gas inlet 18. The raw material gas 200 consists of CH4 and CO2, with a volume ratio of CH4:CO2 = 1:1. A voltage of 0.8V is applied between the anode 1 and the cathode 3.

[0071] When the raw material gas 200 passes through anode 1, CH4 reacts with O2 generated by cathode electrolysis and transported through electrolyte 2. 2- A reaction occurs, producing H2 and CO. The anodic reaction is...

[0072] After the tail gas from the anode enters cathode 3, the CO2 in the mixed gas will undergo an electrolysis reaction, with the cathode reaction being CO2 + 2e-. - →CO+O2- .

[0073] The overall reaction in electrolytic cell 100 is CH4 + CO2 → 2H2 + 2CO. It can be seen that the product gas 300 at cathode 3 is synthesis gas, with a volume ratio of H2 to CO of 1. The product gas is collected at product gas outlet 19.

Claims

1. A method for preparing syngas by high-temperature electrolysis, characterized in that, The method includes: a raw material gas entering the electrolytic cell from the anode inlet; the anode tail gas directly entering the cathode of the electrolytic cell; and finally leaving the electrolytic cell from the cathode outlet; the raw material gas includes hydrocarbon fuel, water vapor, and / or carbon dioxide, and the hydrocarbon fuel includes methane, ethane, propane, methanol, ethanol, and / or biomass gasification gas; the water vapor and / or carbon dioxide in the raw material gas undergo an electrolytic reduction reaction at the cathode to generate hydrogen and / or carbon monoxide, and the hydrocarbon fuel in the raw material gas undergoes a partial oxidation reaction at the anode to generate hydrogen and carbon monoxide.

2. A solid oxide electrolytic reactor for high-temperature electrolytic synthesis of syngas based on the method of claim 1, characterized in that, It includes an anode plate (8), an intermediate plate assembly and a cathode plate (15), wherein the intermediate plate assembly includes a plurality of repeating units, and each repeating unit is connected to the other by a connecting plate (14); The repeating unit includes an anode seal (9), an anode current collector (10), an electrolytic cell (100), a cathode current collector (13), a middle frame (11), and a cathode seal (12) that are sequentially encapsulated. The anode seal (9), the middle frame (11), and the cathode seal middle frame (12) are all hollow frames. The seals encapsulate the electrolytic cell, the current collector, and the middle frame (11) on the connecting plate (14). The anode end plate (8), the repeating unit and the connecting plate (14) are provided with at least one air inlet and one air outlet on the same side, and the repeating unit is provided with at least one opening on the other side; The anode seal (9), the middle frame (11) and the cathode seal (12) are provided with suitable openings on opposite sides to ensure that the anode chamber (16) of the electrolytic cell (100) is connected to the cathode chamber (17), so that the exhaust gas of the anode chamber (16) can directly enter the cathode chamber (17). In the electrolytic cell (100), the raw material gas enters the electrolytic cell from the inlet of the anode (1), the tail gas of the anode directly enters the cathode (3) of the electrolytic cell, and finally leaves the electrolytic cell from the outlet of the cathode (3).

3. The solid oxide electrolytic reactor for high-temperature electrolytic synthesis of syngas according to claim 2, characterized in that, The anode seal (9), the middle frame (11), the cathode seal (12) and the connecting plate (14) are provided with suitable openings on the same side to ensure that the anode chamber (16) in different repeating units is connected to the raw material gas inlet, while the cathode chamber (17) in different repeating units is connected to the product gas outlet.

4. The solid oxide electrolytic reactor for high-temperature electrolytic synthesis of syngas according to claim 2, characterized in that, The anode current collector (10) is filled in the anode chamber (16). The top surface of the anode current collector (10) is in close contact with the bottom surface of the connecting plate (14) or the bottom surface of the anode end plate (8) in the adjacent repeating unit. The bottom surface of the anode current collector (10) is in close contact with the anode (1) of the electrolytic cell (100). The cathode current collector (13) is filled in the cathode chamber (17). The top surface of the cathode current collector (13) is in close contact with the cathode (3) of the electrolytic cell (100). The bottom surface of the cathode current collector (13) is in close contact with the top surface of the connecting plate (14) or the top surface of the cathode end plate (15).

5. The solid oxide electrolytic reactor for high-temperature electrolytic synthesis of syngas according to claim 2, characterized in that, The anode plate (8), middle frame (11), connecting plate (14), and cathode plate (15) are made of high-temperature alloys or conductive oxides with thermal expansion coefficients close to those of the electrolyte, selected from 430L, 441, 446, Crofer, (La 1-x Sr x TiO 3–δ Or La 2-x Sr x Fe 2-y- z Ni y Mo z O 6-δ At least one of the following, wherein the anode current collector (10) and the cathode current collector (13) are made of a metal, alloy, conductive oxide, or a composite thereof with high porosity and good electronic conductivity, selected from nickel foam, nickel felt, nickel mesh, copper foam, copper felt, copper mesh, stainless steel mesh, porous (La) 1-x Sr x TiO 3–δ or porous La 2-x Sr x Fe 2-y-z Ni y Mo z O 6-δ At least one of the following, the surfaces of the anode plate (8), the connecting plate (14), and the cathode plate (15) are covered with a conductive protective coating, the conductive protective coating being selected from Ni, Fe, Co, FeNi3, (La 1-x Sr x (Cr) 1-y Fe y )O 3–δ 、(La 1-x Sr x (Cr) 1-y Mn y )O 3–δ 、(La 1-x Sr x TiO 3–δ Or La 2-x Sr x Fe 2-y-z Ni y Mo z O 6-δ At least one of the following, the anode seal (9) and cathode seal (12) are made of a high-temperature sealing material with high resistivity, selected from glass, mica or vermiculite.

6. The solid oxide electrolytic reactor for high-temperature electrolytic synthesis of syngas according to claim 2, characterized in that, The feedstock gas includes at least two of hydrocarbon fuels, water vapor, and carbon dioxide, wherein the hydrocarbon fuels include at least one of methane, ethane, propane, methanol, ethanol, or biomass gasification gas.

7. The solid oxide electrolytic reactor for high-temperature electrolytic synthesis of syngas according to claim 2, characterized in that, The electrolyte (2) is selected from at least one of yttrium-stabilized zirconium oxide, scandium oxide-stabilized zirconium oxide, cerium oxide doped, strontium magnesium doped lanthanum gallate, barium zirconate doped, or barium cerate doped; the cathode (3) and anode (1) are both composite ceramics comprising an electronically conductive phase and an oxygen ion-conducting phase, wherein the volume fraction of the electronically conductive phase in the solid phase is not less than 40%, and the electronically conductive phase (4) is a metal, alloy, conductive ceramic, or a composite thereof, selected from Ni, Cu, 430L, (La 1-x Sr x (Cr) 1-y Fe y )O 3−δ 、(La 1-x Sr x (Cr) 1-y Mn y )O 3−δ La 2-x Sr x Fe 2-y-z Ni y Mo z O 6-δ Or 430L-(La 1-x Sr x (Cr) 1-y Fe y )O 3−δ At least one of the following, wherein the oxygen ion conducting phase (5) is an oxide with oxygen ion conduction capability, selected from at least one of yttrium-stabilized zirconium oxide, scandium-stabilized zirconium oxide, cerium oxide, strontium magnesium-doped lanthanum gallate, barium zirconate, or barium cerate; the inner wall of the cathode (3) is covered with a nanocatalyst material selected from Ni, Fe, Co, FeNi3, Ce 1-x Sm x O2- δ Ce 1- x Gd x O2- δ 、(La 1-x Sr x (Co) 1-y Fe y )O 3−δ 、(Ba 1-x Sr x (Co) 1-y Fe y )O 3−δ 、(Sm 1-x Sr x CoO 3−δ SmBaCo2O 5+δ LaBa 0.5 Sr 0.5 Co2O 5+δ 、SmBa 0.5 Sr 0.5 Co2O 5+δ 、BaGd 0.8 La 0.2 Co2O 6−δ Or La 2-x Sr x Fe 2-y-z Ni y Mo z O 6-δ At least one of the following, wherein the inner wall of the pores of the anode is covered with a nanocatalyst material selected from Ni, Fe, Co, FeNi3, Ce 1-x Sm x O2- δ Ce 1-x Gd x O2- δ 、(La 1-x Sr x (Co) 1-y Fe y )O 3−δ 、(Ba 1-x Sr x (Co) 1-y Fe y )O 3−δ 、(Sm 1-x Sr x CoO 3−δ SmBaCo2O 5+δ LaBa 0.5 Sr 0.5 Co2O 5+δ 、SmBa 0.5 Sr 0.5 Co2O 5+δ 、BaGd 0.8 La 0.2 Co2O 6−δ Or La 2-x Sr x Fe 2-y- z Ni y Mo z O 6-δ At least one of them.

8. The solid oxide electrolytic reactor for high-temperature electrolytic synthesis of syngas according to claim 2, characterized in that, The operating temperature range of the electrolytic cell (100) is 400-1000℃, and the working voltage between the cathode (3) and the anode (1) is 0.1-2.0V.

9. A high-temperature, high-pressure electrolytic synthesis gas preparation apparatus, characterized in that, The invention includes a high-pressure vessel and a solid oxide electrolytic reactor for high-temperature electrolysis of syngas as described in any one of claims 2-8, wherein the solid oxide electrolytic reactor for high-temperature electrolysis of syngas is placed in the cavity of the high-pressure vessel, and the cavity of the high-pressure vessel is connected to the cathode chamber and the anode chamber of the solid oxide electrolytic reactor for high-temperature electrolysis of syngas.

10. A hydrocarbon fuel synthesis apparatus, characterized in that, The device includes the high-temperature and high-pressure electrolytic synthesis gas preparation apparatus, the fuel high-pressure synthesis module, the thermal management module, and the intelligent control module as described in claim 9. The high-pressure synthesis gas generated by the high-temperature and high-pressure electrolytic synthesis gas preparation apparatus directly enters the fuel high-pressure synthesis module and is converted into hydrocarbon fuel. The thermal management module includes a steam generator, a heat exchanger, and / or an electric heater for preheating the feed gas and recovering the waste heat of the process gas. The hydrocarbon fuel includes methanol, ethanol, gasoline, diesel, and / or sustainable aviation kerosene.

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