Reforming microchannel reactor and solid oxide fuel cell power generation system

Abstract

The invention provides a reforming micro-channel reactor and a solid oxide fuel cell power generation system. The reforming micro-channel reactor comprises a shell, a plurality of plates arranged in the shell, and at least one combustion cavity, at least one heat exchange cavity and at least one reforming reaction cavity which are formed by dividing the interior of the shell by the plates; the combustion chamber, the heat exchange chamber and the reforming reaction chamber are arranged at intervals, and the heat exchange chamber is arranged between the combustion chamber and the reforming reaction chamber; the combustion cavity and the heat exchange cavity are separated by a first plate, and the heat exchange cavity and the reforming reaction cavity are separated by a second plate; each of the first plate and the second plate comprises a ceramic metal composite base material and a catalyst layer loaded on at least one surface of the ceramic metal composite base material, the catalyst layer of the first plate is positioned on one side of the combustion cavity, the catalyst layer of the second plate is positioned on one side of the reforming reaction cavity, and a catalyst of the catalyst layer is a monatomic metal-based catalyst.

Description

Technical Field

[0001] The invention belongs to the technical field of new energy development and utilization and energy conversion, and in particular relates to a reforming microchannel reactor and a solid oxide fuel cell power generation system. Background Art

[0002] The solid oxide fuel cell power generation system (SOFC) is an efficient energy conversion device that can convert chemical energy stored in a variety of gaseous or liquid fuels such as methane, hydrogen, ethanol, and gasoline into electrical energy. It is not limited by the Carnot cycle. Compared with existing traditional gas power plants, it has higher energy efficiency, with a power generation efficiency of up to 60% and a combined heat and power efficiency of up to 90%. It has lower impact on the environment and is considered to be one of the important technologies for achieving energy conservation and emission reduction in the future. In particular, the development of SOFC in the oil and gas industry has many advantages, such as a good gas source foundation, multiple application scenarios, and the integrated development of oil and gas businesses. A large amount of cheap and complex natural gas resources will be generated during the oil and gas production process, which can be used as a high-quality fuel for SOFC power generation.

[0003] However, due to the complex composition of natural gas resources produced during the oil and gas production process, the main components are hydrogen, methane and light hydrocarbon components. If it is used as a raw material and directly enters the SOFC stack, it is easy to cause problems such as carbon deposition, which seriously affects the life of the catalyst and the stack and reduces the power generation efficiency. Usually, a light hydrocarbon component recovery device or a corresponding hydrocarbon external reforming device is required to convert it into synthesis gas before entering the stack system. Hydrocarbon reforming technologies include dry reforming, self-reforming, steam reforming, etc. Among them, steam reforming technology is currently the most mature and industrialized method. However, this technology mainly faces the following problems when applied to SOFC for oil and gas resource development:

[0004] First, the steam reforming reaction represented by methane is a strong endothermic reaction, and a certain pressure (3-5MPa) is required to increase the reaction rate, resulting in high equipment costs and high energy consumption; second, for the reforming of hydrocarbon feedstocks containing high-carbon hydrocarbon components, a pre-reforming and reforming reactor series mode is usually adopted, using different catalysts and reaction conditions, which increases the difficulty of processing and investment and operating costs; third, the heat exchange efficiency between high-temperature flue gas and the reformer is low. In order to achieve the expected heat exchange effect, a reforming device with a larger heat exchange area must be used, resulting in a large system, which is not conducive to the integration of the power generation system and is prone to structural interference with other components in the system; fourth, the system is heavy, which is not conducive to transportation and installation. All of the above have affected the further promotion and application of SOFC power generation systems. How to effectively handle complex natural gas resources in the actual application of SOFC is an urgent problem that technicians in this field need to solve.

[0005] Microchannel reactor technology has been widely used in many fields such as biological analysis, medical diagnosis, and chemical synthesis. With microstructure units as the core, chemical reactions are carried out in micron or submicron confined spaces. By reducing the dispersion scale of the system and strengthening mixing and transfer, it has many advantages such as efficient mixing ability, good mass and heat transfer characteristics, and highly controllable reaction process. The methane steam reforming process uses gas combustion to provide heat for the reforming reaction, which has low heat transfer efficiency, high energy consumption, large equipment, complex structure, high material requirements, and low catalyst effectiveness factor. At the same time, due to heat transfer limitations, the reaction rate is slow. Microchannel reactors can use their high specific surface area to efficiently couple endothermic and exothermic reactions in a small-scale space to strengthen heat and mass transfer. Moreover, microchannel reactors can be amplified in parallel, which not only has no amplification effect, but also can meet the needs of different hydrogen production scales. However, the application of microchannel reactors in solid oxide fuel cells is still rare. However, at present, there are still huge challenges in the use and promotion of microchannel reactors. The main problems are: under high temperature conditions, the catalyst is easy to sinter, the bulk material becomes larger, and the fine pore structure of the microchannel reactor is easily blocked by the solid catalyst and then fails. At the same time, the enlargement of the microchannel reactor often requires increasing the diameter of the microchannel, which is the so-called size enlargement. However, there is an obvious enlargement effect of size enlargement: the increase in channel diameter leads to a decrease in specific surface area and a larger average distance between fluids, which makes the mixing, mass transfer, and heat transfer performances nonlinearly decrease. The above problems limit its large-scale industrial application.

[0006] In summary, there is still a need to study the technical solutions for integrating the use of reforming microchannel reactors in SOFC power generation systems to effectively avoid blockage of microchannel reactors during high-temperature operation, so as to effectively handle the reforming of refinery tail gas with complex components, improve the reforming and heat exchange efficiency in SOFC power generation systems, reduce reaction energy consumption, and improve the integration of SOFC power generation systems. Summary of the invention

[0007] The purpose of the present invention is to provide a technical solution for integrating a reforming reaction to produce synthesis gas microchannel reactor in a SOFC power generation system, which can effectively avoid the blockage of the microchannel reactor during high-temperature operation, thereby effectively processing the reforming of refinery tail gas with complex components, improving the reforming and heat exchange efficiency in the SOFC power generation system, reducing the reaction energy consumption, and improving the integration of the SOFC power generation system. In order to achieve the above purpose, the present invention provides the following two technical solutions:

[0008] In a first aspect, the present invention provides a reforming microchannel reactor, wherein the microchannel reactor comprises a shell and a plurality of plates arranged inside the shell, and at least one combustion chamber, at least one heat exchange chamber and at least one reforming reaction chamber separated by the plates inside the shell;

[0009] The combustion chamber, the heat exchange chamber and the reforming reaction chamber are arranged at intervals, and a heat exchange chamber is arranged between the combustion chamber and the reforming reaction chamber;

[0010] Wherein, the multiple plates include a first plate and a second plate; the combustion chamber and the heat exchange chamber are separated by the first plate, and the heat exchange chamber and the reforming reaction chamber are separated by the second plate; the first plate includes a ceramic-metal composite substrate and a combustion catalyst layer loaded on at least one surface of the ceramic-metal composite substrate, the combustion catalyst layer is located on one side of the combustion chamber, wherein the combustion catalyst of the combustion catalyst layer is a single-atom metal-based catalyst; the second plate includes a ceramic-metal composite substrate and a reforming catalyst layer loaded on at least one surface of the ceramic-metal composite substrate, the reforming catalyst layer is located on one side of the reforming reaction chamber, wherein the reforming catalyst of the reforming catalyst layer is a single-atom metal-based catalyst.

[0011] In the above-mentioned reforming microchannel reactor, the reforming reaction chamber is used for reforming reaction, the combustion chamber is used for fuel catalytic combustion reaction to provide heat for the reforming reaction in the reforming reaction chamber, and the heat exchange chamber serves as a coolant flow channel to transfer the heat generated by fuel combustion to the reforming reaction chamber.

[0012] The reforming microchannel reactor provided in the first aspect of the present invention adopts a combustion chamber, a heat exchange chamber, and a reforming reaction chamber to cooperate in an effective manner to control the heat generated by the combustion chamber to supply the reforming reaction chamber for heating, thereby avoiding excessive temperature in the reforming reaction chamber. At the same time, the catalysts in the combustion chamber and the reforming reaction chamber adopt single-atom metal-based catalysts and are coated on the ceramic surface of the ceramic-metal composite substrate, thereby effectively avoiding the agglomeration and shedding of the catalyst in the microchannel reactor, and solving the problem that the microchannel reactor is prone to blockage during high-temperature operation.

[0013] According to a preferred embodiment of the first aspect, inside the shell, when the combustion chamber serves as the outermost chamber adjacent to the shell, a first plate is arranged between the combustion chamber and the shell, wherein the combustion catalyst layer is located on one side of the combustion chamber.

[0014] According to a preferred embodiment of the first aspect, inside the shell, when the reforming reaction chamber serves as the outermost chamber adjacent to the shell, a second plate is arranged between the reforming reaction chamber and the shell, wherein the reforming catalyst layer is located on one side of the reforming reaction chamber.

[0015] According to a preferred embodiment of the first aspect, a heat-insulating layer is provided inside the shell.

[0016] According to a preferred embodiment of the first aspect, the reforming microchannel reactor is a flat-plate microchannel reactor, and the combustion chamber, the heat exchange chamber and the reforming reaction chamber are arranged inside the shell of the reforming microchannel reactor along the thickness direction of the reforming microchannel reactor;

[0017] Furthermore, a reforming reaction chamber, a heat exchange chamber, a combustion chamber, a heat exchange chamber, a reforming reaction chamber, a heat exchange chamber, a combustion chamber, a heat exchange chamber, a reforming reaction chamber, a heat exchange chamber, a combustion chamber, a heat exchange chamber, a reforming reaction chamber, a heat exchange chamber, and a combustion chamber are sequentially arranged inside the shell of the reforming microchannel reactor along the thickness direction of the reforming microchannel reactor;

[0018] Further, the thickness of the reforming reaction chamber does not exceed 1 mm; further, the thickness of the reforming reaction chamber is 10-1000 μm; in a specific embodiment, the thickness of the reforming reaction chamber is 0.5 mm; controlling the thickness of the reforming reaction chamber to be less than 1 mm can make the reforming reaction chamber have a larger heat exchange specific surface area, which is helpful for timely heat transfer, so that the reforming reaction chamber is always maintained at a higher temperature, so that the reaction can be completed within a residence time of milliseconds;

[0019] Further, the thickness of the heat exchange cavity does not exceed 1 mm; further, the thickness of the heat exchange cavity is 10-1000 μm; in a specific embodiment, the thickness of the heat exchange cavity is 0.5 mm;

[0020] Further, the thickness of the combustion chamber does not exceed 1 mm; further, the thickness of the combustion chamber is 10-1000 μm; in a specific embodiment, the thickness of the combustion chamber is 0.5 mm;

[0021] Further, the reforming microchannel reactor adopts a T-shaped, cross-shaped or coaxial ring tube-shaped feeding method;

[0022] Furthermore, the feed port and the discharge port of each chamber of the reforming microchannel reactor are arranged to realize the fluid flow in each chamber of the reforming microchannel reactor adopting a one-way staggered flow; the design of the three chambers of the flat-plate one-way staggered flow combustion chamber, the heat exchange chamber, and the reforming reaction chamber can effectively control the reforming reaction temperature while realizing an efficient heat transfer reaction, and the temperature can be controlled according to different components.

[0023] Furthermore, the feed inlet and the discharge outlet of each cavity of the reforming microchannel reactor are arranged so as to realize the cross-shaped staggered flow of the fluid flow in each cavity of the reforming microchannel reactor; for example, the flow direction of the fluid in each cavity arranged along the thickness direction of the reforming microchannel reactor inside the shell of the reforming microchannel reactor is alternately along the length direction of the reforming microchannel reactor and along the width direction of the reforming microchannel reactor, that is, assuming that the cavities inside the shell of the reforming microchannel reactor are named the first cavity, the second cavity to the Nth cavity in sequence along the thickness direction of the reforming microchannel reactor, when the fluid in the i-th cavity flows along the length direction of the reforming microchannel reactor, the fluid in the i+1th cavity flows along the width direction of the reforming microchannel reactor, the fluid in the i+2th cavity flows along the length direction of the reforming microchannel reactor, and the fluid in the i+3th cavity flows along the width direction of the reforming microchannel reactor…

[0024] According to a preferred embodiment of the first aspect, the ceramic-metal composite substrate of the first plate material is composed of a metal plate inner core and a ceramic shell composited on the surface of the metal plate; further, the thickness of the metal plate inner core of the ceramic-metal composite substrate of the first plate material does not exceed 2 cm, and the thickness of the ceramic shell composited on the surface of the metal plate does not exceed 50 μm.

[0025] According to a preferred embodiment of the first aspect, the ceramic-metal composite substrate of the second plate material is composed of a metal plate inner core and a ceramic shell composited on the surface of the metal plate; further, the thickness of the metal plate inner core of the ceramic-metal composite substrate of the second plate material does not exceed 2 cm, and the thickness of the ceramic shell composited on the surface of the metal plate does not exceed 50 μm.

[0026] According to a preferred embodiment of the first aspect, wherein the combustion catalyst is a Pt-based catalyst;

[0027] Further, the combustion catalyst is a Pt / Al2O3 catalyst;

[0028] Furthermore, based on 100% by mass of Al2O3, the loading amount of Pt does not exceed 4%.

[0029] According to a preferred embodiment of the first aspect, wherein the reforming catalyst is an Rh-based catalyst;

[0030] Further, the reforming catalyst is a Rh / Al2O3 catalyst;

[0031] Furthermore, based on 100% by mass of Al2O3, the loading amount of Rh does not exceed 4%.

[0032] According to a preferred embodiment of the first aspect, the first plate can be prepared by the following method:

[0033] Aluminum oxide is sprayed onto a metal plate by thermal spraying to form a ceramic-metal composite substrate; the ceramic-metal composite substrate is pretreated, including cutting, cleaning, ultrasonic treatment, etc.; aluminum sol is coated on the surface of the pretreated ceramic-metal composite substrate to obtain a first substrate;

[0034] Weigh a certain amount of an active metal precursor salt corresponding to a combustion catalyst (when the combustion catalyst is a Pt-based catalyst, the active metal precursor acetate salt is selected from platinum acetate), an organic ligand and an organic solvent, and mix them to obtain a first solution;

[0035] Using the first solution to impregnate at least one surface of the first substrate, drying, and calcining under a protective atmosphere to obtain a first plate;

[0036] Further, the active metal precursor salt includes one or a combination of two or more of active metal precursor nitrate, active metal precursor sulfate, active metal precursor chloride, and active metal precursor acetate;

[0037] Further, the organic ligand includes at least one of o-phenanthroline, 2,2-bipyridine, melamine and phenylalanine;

[0038] Further, the organic solvent includes at least one of dimethyl sulfoxide and ethanol;

[0039] Further, in the first solution, the molar ratio of the active metal precursor salt to the organic ligand is 1:5-1:20;

[0040] Furthermore, in the first solution, based on the total volume of the first solution, the molar concentration of the active metal precursor salt is no more than 0.2 mol·L -1 ;

[0041] Furthermore, in the first solution, based on the total volume of the first solution, the molar concentration of the organic ligand is no more than 4 mol·L -1 ;

[0042] Further, in the process of using thermal spraying to spray aluminum oxide on a metal plate to form a ceramic-metal composite substrate, the combustion gas is oxygen, the fuel gas is acetylene, the auxiliary gas is compressed air, the combustion gas pressure is 0.3-1.0 MPa, the fuel gas pressure is 0.05-0.3 MPa, the auxiliary gas pressure is 0.3-1.0 MPa, the powder feeding rate is 10-100 g / min, the spraying distance is 50-200 mm, the flame spray gun moving speed is 100-1200 mm / s, and the number of coating spraying times is 1-30 times;

[0043] Further, the protective atmosphere includes argon atmosphere and / or nitrogen atmosphere;

[0044] Furthermore, the calcination temperature is 300-800° C., and the calcination time at the calcination temperature is 1-5 hours;

[0045] Furthermore, the heating rate during the roasting process to the roasting temperature is 2-10°C / min;

[0046] Furthermore, the drying is heating drying; in a specific embodiment, the drying includes heating in a 60° C. water bath for 4 h, and then maintaining in an oven at 80° C. for 12 h.

[0047] According to a preferred embodiment of the first aspect, the second plate can be prepared by the following method:

[0048] Aluminum oxide is sprayed onto a metal plate by thermal spraying to form a ceramic-metal composite substrate; the ceramic-metal composite substrate is pretreated, including cutting, cleaning, ultrasonic treatment, etc.; aluminum sol is coated on the surface of the pretreated ceramic-metal composite substrate to obtain a second substrate;

[0049] Weigh a certain amount of active metal precursor salt corresponding to the reforming catalyst (when the reforming catalyst is an Rh-based catalyst, the metal precursor acetate salt is rhodium acetate), an organic ligand and an organic solvent, and mix them to obtain a second solution;

[0050] impregnating at least one surface of the second substrate with a second solution, drying, and calcining under a protective atmosphere to obtain a second plate;

[0051] Further, the active metal precursor salt includes one or a combination of two or more of active metal precursor nitrate, active metal precursor sulfate, active metal precursor chloride, and active metal precursor acetate;

[0052] Further, the organic ligand includes at least one of o-phenanthroline, 2,2-bipyridine, melamine and phenylalanine; further, the organic solvent includes at least one of dimethyl sulfoxide and ethanol;

[0053] Further, the organic solvent includes at least one of dimethyl sulfoxide and ethanol;

[0054] Further, in the second solution, the molar ratio of the active metal precursor salt to the organic ligand is 1:5-1:20;

[0055] Furthermore, in the second solution, based on the total volume of the second solution, the molar concentration of the active metal precursor salt does not exceed 0.2 mol·L -1 ;

[0056] Furthermore, in the second solution, based on the total volume of the second solution, the molar concentration of the organic ligand is no more than 4 mol·L -1 ;

[0057] Further, in the process of using thermal spraying to spray aluminum oxide on a metal plate to form a ceramic-metal composite substrate, the combustion gas is oxygen, the fuel gas is acetylene, the auxiliary gas is compressed air, the combustion gas pressure is 0.3-1.0 MPa, the fuel gas pressure is 0.05-0.3 MPa, the auxiliary gas pressure is 0.3-1.0 MPa, the powder feeding rate is 10-100 g / min, the spraying distance is 50-200 mm, the flame spray gun moving speed is 100-1200 mm / s, and the number of coating spraying times is 1-30 times;

[0058] Further, the protective atmosphere includes argon atmosphere and / or nitrogen atmosphere;

[0059] Furthermore, the calcination temperature is 300-800° C., and the calcination time at the calcination temperature is 1-5 hours;

[0060] Furthermore, the heating rate during the roasting process to the roasting temperature is 2-10°C / min;

[0061] Furthermore, the drying is heating drying; in a specific embodiment, the drying includes heating in a 60° C. water bath for 4 h, and then maintaining in an oven at 80° C. for 12 h.

[0062] According to a preferred embodiment of the first aspect, the reforming microchannel reactor further comprises a coolant located inside the heat exchange cavity; the coolant is selected from molten salt;

[0063] Furthermore, the coolant is selected from LiF-NaF-KF molten salt or KCl-MgCl2 molten salt or NaNO3-NaNO2-KNO3 molten salt;

[0064] Furthermore, the coolant is selected from KCl-MgCl2 molten salt;

[0065] Molten salts, especially LiF-NaF-KF molten salts, KCl-MgCl2 molten salts, and NaNO3-NaNO2-KNO3 molten salts, have excellent chemical and heat transfer properties under high temperature conditions, among which KCl-MgCl2 molten salt has the best performance.

[0066] According to a preferred embodiment of the first aspect, temperature detectors (such as thermocouple temperature detectors) are provided at the reforming reaction feed inlet and the reforming reaction discharge port of the reforming microchannel reactor to detect the temperature of the fluid entering and exiting the reforming reaction chamber; this helps to evaluate the temperature inside the reforming reaction chamber.

[0067] According to a preferred embodiment of the first aspect, the heat exchange chamber is externally connected to a temperature and flow control device for regulating the flow of the coolant in the heat exchange chamber, thereby regulating the temperature of the reforming reaction chamber. For example, the temperature and flow control device includes a temperature feedback module, which determines the temperature inside the reforming reaction chamber through the temperature feedback module, and then an automatic control program adjusts the coolant flow, thereby regulating the temperature of the heat exchange chamber.

[0068] According to a preferred embodiment of the first aspect, a temperature sensor is provided in the heat exchange cavity.

[0069] In a second aspect, the present invention provides a solid oxide fuel cell power generation system, the system comprising:

[0070] A material supply unit for reforming, a deionized water supply unit, an air supply unit, a fuel supply unit, a microchannel reactor reforming synthesis gas production unit and a solid oxide fuel cell; the microchannel reactor reforming synthesis gas production unit comprises at least one reforming microchannel reactor provided by the first aspect of the present invention;

[0071] Among them, the connection relationship between the material supply unit to be reformed, the deionized water supply unit, the air supply unit, the fuel supply unit, the microchannel reactor reforming synthesis gas production unit and the solid oxide fuel cell can be achieved: the material supply unit to be reformed supplies the material to be reformed required for the reforming reaction to the microchannel reactor reforming synthesis gas production unit, the deionized water supply unit supplies the water vapor required for the reforming reaction to the microchannel reactor reforming synthesis gas production unit, the fuel supply unit supplies the fuel required for the catalytic combustion reaction to the microchannel reactor reforming synthesis gas production unit, the air supply unit supplies air to the cathode of the solid oxide fuel cell, and the synthesis gas produced by the reforming reaction of the microchannel reactor reforming synthesis gas production unit is supplied to the anode of the solid oxide fuel cell (that is, the reforming reaction outlet of the reforming reaction of the microchannel reactor reforming synthesis gas production unit is connected to the anode air inlet of the solid oxide fuel cell).

[0072] The solid oxide fuel cell power generation system provided in the second aspect of the present invention adopts the special reforming microchannel reactor provided in the first aspect of the present invention, and realizes the integration of the reforming reaction to produce synthesis gas microchannel reactor in the SOFC power generation system, while effectively avoiding the blockage of the microchannel reactor during high-temperature operation. It can effectively handle the reforming of refinery tail gas with complex components, improve the reforming and heat exchange efficiency in the SOFC power generation system, reduce the reaction energy consumption, and improve the integration of the SOFC power generation system.

[0073] According to a preferred embodiment of the second aspect, the system further comprises: a heat exchange unit, the heat exchange unit comprising a first heat exchanger, a second heat exchanger, a third heat exchanger, a fourth heat exchanger, a fifth heat exchanger and a sixth heat exchanger;

[0074] The first fluid inlet of the first heat exchanger is connected to the outlet of the supply unit for the material to be reformed, the first fluid outlet of the first heat exchanger is connected to the first fluid inlet of the fourth heat exchanger, and the first fluid outlet of the fourth heat exchanger is connected to the reforming reaction feed port of the microchannel reactor reforming synthesis gas unit; the first fluid inlet of the second heat exchanger is connected to the outlet of the deionized water supply unit, and the first fluid outlet of the second heat exchanger is connected to the reforming reaction feed port of the microchannel reactor reforming synthesis gas unit; the first fluid inlet of the third heat exchanger is connected to the outlet of the air supply unit, the first fluid outlet of the third heat exchanger is connected to the first fluid inlet of the fifth heat exchanger, and the first fluid outlet of the fifth heat exchanger is connected to the cathode air inlet of the solid oxide fuel cell; the sixth heat exchanger The first fluid inlet of the heat exchanger is connected to the outlet of the fuel supply unit, the first fluid outlet of the sixth heat exchanger is connected to the catalytic combustion reaction feed port of the microchannel reactor reforming synthesis gas production unit; the second fluid inlet of the third heat exchanger is connected to the anode tail outlet of the solid oxide fuel cell, the second fluid outlet of the third heat exchanger is connected to the second fluid inlet of the second heat exchanger, and the second fluid outlet of the second heat exchanger is connected to the second fluid inlet of the first heat exchanger; the catalytic combustion reaction discharge port of the microchannel reactor reforming synthesis gas production unit is connected to the second fluid inlet of the fourth heat exchanger, the second fluid outlet of the fourth heat exchanger is connected to the second fluid inlet of the sixth heat exchanger, and the cathode tail outlet of the solid oxide fuel cell is connected to the second fluid inlet of the fifth heat exchanger;

[0075] Further, the second fluid outlet of the first heat exchanger is connected to the second fluid inlet of the sixth heat exchanger; further, a gas-water separator is provided on the connecting pipeline between the second fluid outlet of the first heat exchanger and the second fluid inlet of the sixth heat exchanger to remove moisture from the fluid;

[0076] Furthermore, the second fluid outlet of the first heat exchanger is connected to the catalytic combustion reaction feed inlet of the microchannel reactor reforming synthesis gas production unit.

[0077] According to a preferred embodiment of the second aspect, the microchannel reactor reforming synthesis gas production unit includes at least two reforming microchannel reactors provided by the first aspect of the present invention, and each reforming microchannel reactor is connected in series in sequence, wherein the reforming reaction discharge port of the i-th reforming microchannel reactor is connected to the reforming reaction feed port of the i+1-th reforming microchannel reactor, the coolant feed port of the i-th reforming microchannel reactor is connected to the coolant discharge port of the i+1-th reforming microchannel reactor, the catalytic combustion reaction feed port of the i-th reforming microchannel reactor is connected to the catalytic combustion reaction discharge port of the i+1-th reforming microchannel reactor, and the catalytic combustion reaction discharge port of the first reforming microchannel reactor serves as the microchannel reactor reforming synthesis gas production unit. The catalytic combustion reaction outlet of the synthesis gas unit, the catalytic combustion reaction feed port of the last reforming microchannel reactor serves as the catalytic combustion reaction feed port of the microchannel reactor reforming synthesis gas unit, the reforming reaction outlet of the last reforming microchannel reactor serves as the reforming reaction outlet of the microchannel reactor reforming synthesis gas unit, the reforming reaction feed port of the first reforming microchannel reactor serves as the reforming reaction feed port of the microchannel reactor reforming synthesis gas unit, the coolant outlet of the first reforming microchannel reactor serves as the coolant outlet of the microchannel reactor reforming synthesis gas unit, and the coolant outlet of the last reforming microchannel reactor serves as the coolant outlet of the microchannel reactor reforming synthesis gas unit.

[0078] According to a preferred embodiment of the second aspect, the material supply unit for reforming includes a desulfurizer, the inlet of the desulfurizer is connected to the source of the material to be reformed, and the outlet of the desulfurizer serves as the outlet of the material supply unit for reforming.

[0079] According to a preferred embodiment of the second aspect, the deionized water supply unit comprises a water pump, an inlet of the water pump is connected to a deionized water source, and an outlet of the water pump serves as an outlet of the deionized water supply unit.

[0080] According to a preferred embodiment of the second aspect, the air supply unit comprises an air compressor, an inlet of the air compressor is connected to an air source, and an outlet of the air compressor serves as an outlet of the air supply unit.

[0081] Compared with the prior art, the technical solution provided by the present invention has the following beneficial effects:

[0082] 1. The reforming microchannel reactor provided by the present invention adopts a combustion chamber, a heat exchange chamber, and a reforming reaction chamber in a coordinated manner. At the same time, the catalysts in the combustion chamber and the reforming reaction chamber adopt single-atom metal-based catalysts and are coated on the ceramic surface of the ceramic-metal composite substrate, thereby effectively avoiding the agglomeration and shedding of the catalyst in the microchannel reactor, and solving the problem that the microchannel reactor is prone to blockage during high-temperature operation.

[0083] 2. The microchannel reactor provided by the present invention has high energy conversion efficiency and good heat and mass transfer performance, which significantly improves the heat transfer and reaction efficiency of the reforming reaction and realizes efficient and rapid reforming.

[0084] 3. The microchannel reactor provided by the present invention adopts a three-channel design of combustion chamber, heat exchange chamber and reforming reaction chamber, which can effectively control the reforming reaction temperature while achieving efficient heat transfer reaction, which is conducive to the reforming treatment of raw materials with different components.

[0085] 4. The reforming microchannel reactor provided by the present invention has adjustable denaturation of reactants and products. By regulating the type of coated catalyst layer and the flow rate of coolant, the reforming microchannel reactor provided by the present invention can withstand different types of reaction raw materials in complex gas resources, methane and other light hydrocarbon components, etc. At the same time, the reforming microchannel reactor can achieve both efficient hydrogen production and efficient synthesis gas. In addition, the reforming microchannel reactor provided by the present invention can withstand a certain reaction pressure, which will further improve the reaction efficiency, and its use in solid oxide fuel cell power generation systems can broaden the application of SOFC systems.

[0086] 5. The solid oxide fuel cell power generation system provided by the present invention uses the microchannel reactor provided by the present invention to carry out reforming reaction. The microchannel reactor has many advantages such as small size, light weight, high strength, high heat transfer efficiency, low leakage rate, strong corrosion resistance without solder, and high weld reliability. At the same time, the microchannel reactor is resistant to high pressure, high temperature, corrosion, and has a long service life. The use of the microchannel reactor effectively improves the integration of the solid oxide fuel cell power generation system, helps to streamline the solid oxide fuel cell power generation system equipment, reduce the system weight, and reduce the system cost.

[0087] 6. The solid oxide fuel cell power generation system provided by the present invention uses the microchannel reactor provided by the present invention, and can achieve the scale-up of the raw gas supply without a step-by-step amplification device. This makes the solid oxide fuel cell power generation system provided by the present invention match power generation application scenarios of different scales, and can be used in large-scale power generation devices such as data center power supply and refinery power supply, and can also be used in small-scale stable energy supply systems such as aerospace and vehicle and ship power systems.

[0088] 7. The solid oxide fuel cell power generation system provided by the present invention has flexible and adjustable properties, and can be flexibly matched with a variety of energy supply devices. Later, it can not only be connected in series with the SOFC power generation system, but also can be flexibly matched in series with PEMFC or MCFC, and used as a fuel cell vehicle power device, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0089] Figure 1 This is a schematic diagram of the structure of the solid oxide fuel cell power generation system of Example 1.

[0090] Figure 2 This is a schematic diagram of the structure of the microchannel reactor reforming synthesis gas production unit in Example 1.

[0091] Figure 3 This is a schematic diagram of the structure of the first plate in Example 1. DETAILED DESCRIPTION

[0092] In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be construed as limiting the applicable scope of the present invention.

[0093] Example 1

[0094] This embodiment provides a solid oxide fuel cell power generation system, such as Figure 1 As shown, the separation system includes a material supply unit for reforming, a deionized water supply unit, an air supply unit, a fuel supply unit, a heat exchange unit, a microchannel reactor reforming synthesis gas production unit and a solid oxide fuel cell 1.

[0095] like Figure 2As shown, the microchannel reactor reforming synthesis gas production unit includes a first reforming microchannel reactor 21 and a second reforming microchannel reactor 22 connected in series. The first reforming microchannel reactor 21 and the second reforming microchannel reactor 22 are both flat-plate microchannel reactors, and both include a shell 201, a first plate 202 and a second plate 203 arranged inside the shell, and a combustion chamber 204, a heat exchange chamber 205 and a reforming reaction chamber 206 separated by the first plate 202 and the second plate 203 inside the shell 201, the reforming reaction chamber 206 is used for reforming reaction, the combustion chamber 204 is used for catalytic combustion reaction of fuel to provide heat for the reforming reaction in the reforming reaction chamber 206, and the heat exchange chamber 205 is used as a coolant circulation channel to transfer the heat generated by the combustion of the fuel to the reforming reaction chamber 206; wherein, the reforming reaction chamber 206, the heat exchange chamber 205, the combustion chamber 204, the heat exchange chamber 205, the reforming reaction chamber 206, the heat exchange chamber 205, the combustion chamber 204, the heat exchange chamber 205, the reforming reaction chamber 206, the heat exchange chamber 205, and the combustion chamber 204 are arranged in sequence along the thickness direction of the reforming microchannel reactor. The thickness of the reforming reaction chamber is 0.5 mm, the thickness of the combustion chamber is 0.5 mm, and the thickness of the heat exchange chamber is 0.5 mm. The feed port and the discharge port of each chamber of the reforming microchannel reactor are set to realize that the fluid flow in each chamber of the reforming microchannel reactor adopts a one-way cross-shaped staggered flow. Specifically, the fluid flow direction in each combustion chamber 204, heat exchange chamber 205 and reforming reaction chamber 206 arranged along the thickness direction of the reforming microchannel reactor inside the shell 201 is alternately carried out along the length direction of the reforming microchannel reactor and along the width direction of the reforming microchannel reactor. The combustion chamber 204 and the heat exchange chamber 205 are separated by a first plate 202, and the heat exchange chamber 205 and the reforming reaction chamber 206 are separated by a second plate 203. The first plate 202 is set between the outermost combustion chamber 204 adjacent to the shell 201 and the shell 201, and the combustion catalyst layer is located on one side of the combustion chamber 204. A second plate 203 is disposed between the outermost reforming reaction chamber 206 adjacent to the shell 201 and the shell 201 , and the reforming catalyst layer is located on one side of the reforming reaction chamber 206 .

[0096] The first plate 202 includes a ceramic-metal composite substrate and a combustion catalyst layer (such as Figure 3As shown), the combustion catalyst of the combustion catalyst layer is a single-atom metal-based catalyst, specifically a Pt / Al2O3 catalyst, with a loading of 4%. The second plate 203 includes a ceramic-metal composite substrate and a reforming catalyst layer loaded on the surface of the ceramic-metal composite substrate. The reforming catalyst of the reforming catalyst layer is a single-atom metal-based catalyst, specifically a Rh / Al2O3 catalyst, with a loading of 4%. The ceramic-metal composite substrate of the first plate 202 and the ceramic-metal composite substrate of the second plate 203 are both composed of a FeCrAl alloy metal plate inner core and a ceramic shell composited on the surface of the metal plate. The thickness of the metal plate inner core of the ceramic-metal composite substrate of the first plate is 0.7 mm, and the thickness of the ceramic shell composited on the surface of the metal plate is 10 microns. The thickness of the metal plate inner core of the ceramic-metal composite substrate of the second plate is 0.7 mm, and the thickness of the ceramic shell composited on the surface of the metal plate is 10 microns. Among them, the first plate 202 can be prepared by the following method: using thermal spraying to spray aluminum oxide on a metal plate to form a ceramic-metal composite substrate (in the process, the combustion gas is oxygen, the fuel gas is acetylene, the auxiliary gas is compressed air, the combustion gas pressure is 0.3-1.0MPa, the fuel gas pressure is 0.05-0.3MPa, the auxiliary gas pressure is 0.3-1.0MPa, the powder feeding rate is 10-100g / min, the spraying distance is 50-200mm, the flame spray gun moving speed is 100-1200mm / s, and the number of coating spraying times is 1-30 times); for ceramic The metal composite substrate is pretreated, including cutting, cleaning, ultrasonic treatment and the like; aluminum sol (thickness 10 μm) is coated on the surface of the pretreated ceramic metal composite substrate to obtain a first substrate; 0.2 mmol of platinum acetate, 1 mmol of o-phenanthroline and 100 ml of ethanol are weighed and mixed to obtain a first solution; the first substrate is immersed in the first solution, heated in a 60°C water bath for 4 hours, then maintained at 80°C in an oven for 12 hours, then heated to 750°C at 5°C / min in an argon atmosphere and calcined at 750°C for 4 hours, then naturally cooled to room temperature to obtain a first plate.Among them, the second plate 203 can be prepared by the following method: using thermal spraying to spray aluminum oxide on a metal plate to form a ceramic-metal composite substrate (in the process, the combustion gas is oxygen, the fuel gas is acetylene, the auxiliary gas is compressed air, the combustion gas pressure is 0.3-1.0MPa, the fuel gas pressure is 0.05-0.3MPa, the auxiliary gas pressure is 0.3-1.0MPa, the powder feeding rate is 10-100g / min, the spraying distance is 50-200mm, the flame spray gun moving speed is 100-1200mm / s, and the number of coating spraying times is 1-30 times); for ceramic The metal composite substrate is pretreated, including cutting, cleaning, ultrasonic treatment and the like; aluminum sol (thickness 10 μm) is coated on the surface of the pretreated ceramic metal composite substrate to obtain a second substrate; 0.2 mmol of rhodium acetate, 1 mmol of o-phenanthroline and 100 ml of ethanol are weighed and mixed to obtain a second solution; the second substrate is immersed in the second solution, heated in a 60°C water bath for 4 hours, then maintained at 80°C in an oven for 12 hours, then heated to 750°C at 5°C / min in an argon atmosphere and calcined at 750°C for 4 hours, then naturally cooled to room temperature to obtain a second plate.

[0097] The first reforming microchannel reactor 21 and the second reforming microchannel reactor 22 are both provided with a first reforming reaction feed port 207, a second reforming reaction feed port 208, a reforming reaction discharge port 209, a coolant feed port 210, a coolant discharge port 211, a catalytic combustion reaction feed port 212, and a catalytic combustion reaction discharge port 213. The reforming reaction discharge port 209 of the first reforming microchannel reactor 21 is connected to the reforming reaction feed port 208 of the second reforming microchannel reactor 22, and a one-way valve 214 is provided on the connecting pipeline, the coolant feed port 210 of the first reforming microchannel reactor 21 is connected to the coolant discharge port 211 of the second reforming microchannel reactor 22, and the catalytic combustion reaction feed port 212 of the first reforming microchannel reactor 21 is connected to the catalytic combustion reaction discharge port 213 of the second reforming microchannel reactor 22.

[0098] A heat-insulating layer 2012 is provided inside the shell 201 .

[0099] The coolant located inside the heat exchange chamber 205 is KCl-MgCl2 molten salt.

[0100] The first reforming reaction feed port 207, the second reforming reaction feed port 208, and the reforming reaction discharge port 209 are provided with temperature detectors (such as thermocouple temperature detectors) for detecting the temperature of the fluid entering and exiting the reforming reaction chamber, which helps to evaluate the temperature inside the reforming reaction chamber.

[0101] The coolant inlet 210 and the coolant outlet 211 are externally connected to a temperature and flow control device 23 for regulating the flow of the coolant in the heat exchange chamber 205, thereby achieving regulation of the temperature of the reforming reaction chamber.

[0102] The material supply unit for reforming includes a desulfurizer 41, the inlet of which is connected to a source of the material to be reformed. The deionized water supply unit includes a water pump 51, the inlet of which is connected to a source of deionized water. The air supply unit includes an air compressor 61, the inlet of which is connected to an air source.

[0103] The heat exchange unit includes a first heat exchanger 31, a second heat exchanger 32, a third heat exchanger 33, a fourth heat exchanger 34, a fifth heat exchanger 35 and a sixth heat exchanger 36;

[0104] The first fluid inlet of the first heat exchanger 31 is connected to the outlet of the desulfurizer 41, the first fluid outlet of the first heat exchanger 31 is connected to the first fluid inlet of the fourth heat exchanger 34, and the first fluid outlet of the fourth heat exchanger 34 is connected to the first reforming reaction feed port 207 of the first reforming microchannel reactor 21; the first fluid inlet of the second heat exchanger 32 is connected to the outlet of the water pump 51, and the first fluid outlet of the second heat exchanger 32 is connected to the second reforming reaction feed port 208 of the first reforming microchannel reactor 21; the first fluid inlet of the third heat exchanger 33 is connected to the outlet of the air compressor 61, the first fluid outlet of the third heat exchanger 33 is connected to the first fluid inlet of the fifth heat exchanger 35, and the first fluid outlet of the fifth heat exchanger 35 is connected to the cathode air inlet of the solid oxide fuel cell 1; the first fluid inlet of the sixth heat exchanger 36 is connected to the outlet of the fuel supply unit, and the first fluid outlet of the sixth heat exchanger 36 is connected to the catalytic combustion reaction feed port 212 of the second reforming microchannel reactor 22; The second fluid inlet of the heat exchanger 33 is connected to the anode tail outlet of the solid oxide fuel cell 1, the second fluid outlet of the third heat exchanger 33 is connected to the second fluid inlet of the second heat exchanger 32, and the second fluid outlet of the second heat exchanger 32 is connected to the second fluid inlet of the first heat exchanger 31; the catalytic combustion reaction outlet 213 of the first reforming microchannel reactor 21 is connected to the second fluid inlet of the fourth heat exchanger 34, the second fluid outlet of the fourth heat exchanger 34 is connected to the second fluid inlet of the sixth heat exchanger 36, and the cathode tail outlet of the solid oxide fuel cell 1 is connected to the second fluid inlet of the fifth heat exchanger 35; the second fluid outlet of the first heat exchanger 31 is connected to the second fluid inlet of the sixth heat exchanger 36; a gas-water separator 7 is provided on the connecting pipeline between the second fluid outlet of the first heat exchanger 31 and the second fluid inlet of the sixth heat exchanger 36 to remove moisture from the fluid; the second fluid outlet of the first heat exchanger 31 is connected to the catalytic combustion reaction feed inlet 212 of the second reforming microchannel reactor 22.

[0105] Experimental Example 1

[0106] The solid oxide fuel cell power generation system provided in Example 1 is used to generate electricity, wherein the materials to be reformed are the raw gas from refinery A, the raw gas from refinery B, and the raw gas from refinery C described in Table 1, respectively; according to the characteristics of the composition of the raw gas from refinery A, the raw gas from refinery B, and the raw gas from refinery C, the first reforming microchannel reactor 21 is closed and the second reforming microchannel reactor 22 is operated by controlling the one-way valve 214 between the first reforming microchannel reactor 21 and the second reforming microchannel reactor 22, and the raw gas enters the solid oxide fuel cell 1 to generate electricity after being reformed to prepare synthesis gas in the reforming synthesis gas production unit of the microchannel reactor.

[0107] The anode feed gas inlet pressure of the solid oxide fuel cell 1 is controlled at 200-300 kPa and the flow rate is controlled at 60 Nm 3 / h, temperature is 25°C; the cathode feed gas inlet pressure of the solid oxide fuel cell 1 is controlled at 200-300 kPa, and the flow rate is controlled at 600 Nm 3 / h, temperature is 25℃; the corresponding fuel cell system power generation is 100 kW. The fuel required for the catalytic combustion reaction is SOFC anode tail gas.

[0108] The simulation results of COMSOL and Aspen are shown in Table 2. Two system operation times were selected for characterization. When the system operation time was 1 hour, the flow rate at the inlet and outlet of the microreactor remained unchanged; when the system maintained a long-term operation for 1000 hours, the flow rate at the outlet of the microreactor remained basically unchanged, with a decay rate of about 0.03%, confirming that the microreactor can still maintain normal operation during the long-term operation. Under the conditions of this embodiment, the system power generation efficiency is about 51.45%.

[0109] Table 1

[0110]

[0111] Table 2 Simulation results of Example 1

[0112]

[0113] Experimental Example 2:

[0114] The solid oxide fuel cell power generation system provided in Example 1 is used for power generation, wherein the materials to be reformed are respectively the raw gas of refinery D, the raw gas of refinery E, and the raw gas of refinery F as described in Table 3; according to the characteristics of the raw gas composition of refinery D, refinery E, and refinery F, the one-way valve 214 between the first reforming microchannel reactor 21 and the second reforming microchannel reactor 22 is controlled to make the first reforming microchannel reactor 21 and the second reforming microchannel reactor 22 operate in parallel, and the raw gas enters the solid oxide fuel cell 1 for power generation after being reformed and prepared into syngas by the microchannel reactor reforming syngas production unit. At the same time, the temperature and flow control device 23 is used to control the temperature of the first reforming microchannel reactor 21 and the second reforming microchannel reactor 22, so that they are in their respective reasonable operating ranges.

[0115] The anode feed gas inlet pressure of the solid oxide fuel cell 1 is controlled at 200-300 kPa and the flow rate is controlled at 60 Nm 3 / h, temperature is 25°C; the cathode feed gas inlet pressure of the solid oxide fuel cell 1 is controlled at 200-300kpa, and the flow rate is controlled at 600Nm 3 / h, temperature is 25℃; the corresponding fuel cell system power generation is 100kW. The fuel required for the catalytic combustion reaction is SOFC anode tail gas.

[0116] The simulation results of COMSOL and Aspen are shown in Table 4. Two system operation times were selected for characterization. When the system operation time was 1 hour, the flow rate at the inlet and outlet of the microreactor remained unchanged; when the system maintained a long-term operation for 1000 hours, the flow rate at the outlet of the microreactor remained basically unchanged, with a decay rate of about 0.8%, confirming that the microreactor can still maintain normal operation during the long-term operation. Under the conditions of this embodiment, the system power generation efficiency is about 52.33%.

[0117] Table 3

[0118]

[0119] Table 4 Simulation results of Example 2

[0120]

[0121] Experimental Example 3:

[0122] The solid oxide fuel cell power generation system provided in Example 1 is used to generate electricity, wherein hydrogen is used as the material to be reformed, and the first reforming microchannel reactor 21 and the second reforming microchannel reactor 22 are closed, so that the hydrogen is heated by the heat exchanger and then directly enters the solid oxide fuel cell 1 to generate electricity.

[0123] The anode feed gas inlet pressure of the solid oxide fuel cell 1 is controlled at 200-300 kPa and the flow rate is controlled at 60 Nm 3 / h, temperature is 25°C; the cathode feed gas inlet pressure of the solid oxide fuel cell 1 is controlled at 200-300kpa, and the flow rate is controlled at 600Nm 3 / h, temperature is 25℃; the corresponding fuel cell system power generation is 100kW. The fuel required for the catalytic combustion reaction is SOFC anode tail gas.

[0124] The simulation results of COMSOL and Aspen are shown in Table 5. Since there is no need to use a microreactor for reaction gas reforming, there is no reference value. Under the conditions of this embodiment, the system power generation efficiency is about 49.82%.

[0125] Table 5 Simulation results of Example 3

[0126] Serial number project data 1 The flow rate at the microreactor inlet was measured after the system was operated for 1 hour. / 2 The flow rate at the outlet of the microreactor under the initial conditions of the system running for 1 hour / 3 Microreactor inlet flow rate after 1000 hours of operation / 4 Microreactor outlet flow rate after running for 1000 hours / 5 System power generation efficiency 49.82％

[0127] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

[0128] This comparative example provides a solid oxide fuel cell power generation system, which is different from the solid oxide fuel cell power generation system provided in Example 1 only in that no heat exchange chamber 205 is provided (ie, the combustion chamber 204 and the reforming reaction chamber 206 are adjacent).

[0129] The solid oxide fuel cell power generation system provided in this comparative example was used to generate electricity in the same manner as in Experimental Example 1.

[0130] The results are shown in Table 6. The solid oxide fuel cell power generation system provided in this comparative example was used to generate electricity. After a long period of operation, the system power generation efficiency and outlet flow rate were significantly reduced. The main reason is that the heat exchange chamber is not set, and the temperature of the reforming reaction chamber cannot be effectively controlled, which makes the catalyst run under high temperature conditions, and the pre-reforming and reforming reaction effects are poor, which leads to reduced catalytic efficiency and blockage of the microreactor.

[0131] Table 6

[0132]

[0133] Comparative Example 2

[0134] This comparative example provides a solid oxide fuel cell power generation system. Compared with the solid oxide fuel cell power generation system provided in Example 1, the only difference is that the combustion catalyst layer of the first plate 202 adopts a non-single-atom metal-based catalyst coated on a ceramic-metal composite substrate, and the reforming catalyst layer of the second plate 203 adopts a non-single-atom metal-based catalyst coated on a ceramic-metal composite substrate. For the convenience of simulation, the selected non-single-atom metal-based catalyst is spherical particles with a size of 20nm.

[0135] The solid oxide fuel cell power generation system provided in this comparative example was used to generate electricity in the same manner as in Experimental Example 1.

[0136] The results are shown in Table 7. After a long period of operation, the power generation efficiency and outlet flow rate of the system were significantly reduced by using the solid oxide fuel cell power generation system provided in this comparative example. This is because the non-single atom catalyst itself has poor anti-carbon deposition performance, and the catalyst agglomerates and blocks the microchannel under high temperature conditions.

[0137] Table 7

[0138]

[0139]

[0140] 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 principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A reforming microchannel reactor, wherein: The microchannel reactor comprises a shell and a plurality of plates arranged inside the shell, and at least one combustion chamber, at least one heat exchange chamber and at least one reforming reaction chamber separated by the plates inside the shell; The combustion chamber, the heat exchange chamber and the reforming reaction chamber are arranged at intervals, and a heat exchange chamber is arranged between the combustion chamber and the reforming reaction chamber; Wherein, the multiple plates include a first plate and a second plate; the combustion chamber and the heat exchange chamber are separated by the first plate, and the heat exchange chamber and the reforming reaction chamber are separated by the second plate; the first plate includes a ceramic-metal composite substrate and a combustion catalyst layer loaded on at least one surface of the ceramic-metal composite substrate, the combustion catalyst layer is located on one side of the combustion chamber, wherein the combustion catalyst of the combustion catalyst layer is a single-atom metal-based catalyst; the second plate includes a ceramic-metal composite substrate and a reforming catalyst layer loaded on at least one surface of the ceramic-metal composite substrate, the reforming catalyst layer is located on one side of the reforming reaction chamber, wherein the reforming catalyst of the reforming catalyst layer is a single-atom metal-based catalyst.

2. The reforming microchannel reactor according to claim 1, wherein: Inside the shell, when the combustion chamber is the outermost chamber adjacent to the shell, a first plate is arranged between the combustion chamber and the shell, wherein the combustion catalyst layer is located on one side of the combustion chamber; and / or Inside the shell, when the reforming reaction chamber serves as the outermost chamber adjacent to the shell, a second plate is arranged between the reforming reaction chamber and the shell, wherein the reforming catalyst layer is located at one side of the reforming reaction chamber.

3. The reforming microchannel reactor according to claim 1, wherein: The reforming microchannel reactor is a flat-plate microchannel reactor, and the combustion chamber, the heat exchange chamber and the reforming reaction chamber are arranged inside the shell of the reforming microchannel reactor along the thickness direction of the reforming microchannel reactor; Preferably, a reforming reaction chamber, a heat exchange chamber, a combustion chamber, a heat exchange chamber, a reforming reaction chamber, a heat exchange chamber, a combustion chamber, a heat exchange chamber, a reforming reaction chamber, a heat exchange chamber, a combustion chamber, a heat exchange chamber, a reforming reaction chamber, a heat exchange chamber, and a combustion chamber are sequentially arranged inside the shell of the reforming microchannel reactor along the thickness direction of the reforming microchannel reactor; Preferably, the thickness of the reforming reaction chamber does not exceed 1 mm; more preferably, the thickness of the reforming reaction chamber is 10-1000 μm; Preferably, the thickness of the heat exchange chamber does not exceed 1 mm; more preferably, the thickness of the heat exchange chamber is 10-1000 μm; preferably, the thickness of the combustion chamber does not exceed 1 mm; more preferably, the thickness of the combustion chamber is 10-1000 μm; Preferably, the reforming microchannel reactor adopts a T-shaped, cross-shaped or coaxial ring tube-shaped feeding method; Preferably, the feed inlet and the discharge outlet of each cavity of the reforming microchannel reactor are arranged so as to realize the fluid flow in each cavity of the reforming microchannel reactor adopting a one-way staggered flow; the design of the three cavities of the flat plate type one-way staggered flow combustion cavity, the heat exchange cavity and the reforming reaction cavity can effectively control the reforming reaction temperature while realizing the efficient heat transfer reaction, and the temperature can be controlled according to the different components; Preferably, the feed inlet and the discharge outlet of each chamber of the reforming microchannel reactor are arranged so as to realize a cross-shaped staggered flow of the fluid flow in each chamber of the reforming microchannel reactor.

4. The reforming microchannel reactor according to claim 1, wherein: The ceramic-metal composite substrate of the first plate material is composed of a metal plate inner core and a ceramic outer shell composited on the surface of the metal plate; Preferably, the thickness of the metal plate inner core of the ceramic-metal composite substrate of the first plate material does not exceed 2 cm, and the thickness of the ceramic outer shell composited on the surface of the metal plate does not exceed 50 μm.

5. The reforming microchannel reactor according to claim 1, wherein: The combustion catalyst is a Pt-based catalyst; preferably, the combustion catalyst is a Pt / Al2O3 catalyst; more preferably, the loading amount does not exceed 4% based on 100% by mass of Al2O3.

6. The reforming microchannel reactor according to any one of claims 1, 4 and 5, wherein: The first plate can be prepared by the following method: Aluminum oxide is sprayed onto a metal plate by thermal spraying to form a ceramic-metal composite substrate; the ceramic-metal composite substrate is pretreated, including cutting, cleaning, and ultrasonic treatment; aluminum sol is coated on the surface of the pretreated ceramic-metal composite substrate to obtain a first substrate; Weighing a certain amount of active metal precursor salt corresponding to the combustion catalyst, an organic ligand and an organic solvent and mixing them to obtain a first solution; Using the first solution to impregnate at least one surface of the first substrate, drying, and calcining under a protective atmosphere to obtain a first plate; Preferably, the active metal precursor salt includes one or a combination of two or more of active metal precursor nitrate, active metal precursor sulfate, active metal precursor chloride, and active metal precursor acetate; Preferably, the organic ligand comprises at least one of o-phenanthroline, 2,2-bipyridine, melamine and phenylalanine; Preferably, the organic solvent comprises at least one of dimethyl sulfoxide and ethanol; Preferably, in the first solution, the molar ratio of the active metal precursor salt to the organic ligand is 1:5-1:20; Preferably, in the first solution, based on the total volume of the first solution, the molar concentration of the active metal precursor salt is no more than 0.2 mol·L -1 ; Preferably, in the first solution, the molar concentration of the organic ligand is no more than 4 mol·L -1 .

7. The reforming microchannel reactor according to claim 1, wherein: The ceramic-metal composite substrate of the second plate material is composed of a metal plate inner core and a ceramic outer shell composited on the surface of the metal plate; Preferably, the thickness of the metal plate inner core of the ceramic-metal composite substrate of the second plate material does not exceed 2 cm, and the thickness of the ceramic outer shell composited on the surface of the metal plate does not exceed 50 μm.

8. The reforming microchannel reactor according to claim 1, wherein: The reforming catalyst is a Rh-based catalyst; preferably, the reforming catalyst is a Rh / Al2O3 catalyst; more preferably, based on the mass of Al2O3 being 100%, the V loading amount does not exceed 4%.

9. The reforming microchannel reactor according to any one of claims 1, 7 and 8, wherein: The second plate can be prepared by the following method: Aluminum oxide is sprayed onto a metal plate by thermal spraying to form a ceramic-metal composite substrate; the ceramic-metal composite substrate is pretreated, including cutting, cleaning, and ultrasonic treatment; Coating aluminum sol on the surface of the pretreated ceramic-metal composite substrate to obtain a second substrate; Weighing a certain amount of active metal precursor salt corresponding to the reforming catalyst, an organic ligand and an organic solvent and mixing them to obtain a second solution; impregnating at least one surface of the second substrate with a second solution, drying, and calcining under a protective atmosphere to obtain a second plate; Preferably, the active metal precursor salt includes one or a combination of two or more of active metal precursor nitrate, active metal precursor sulfate, active metal precursor chloride, and active metal precursor acetate; Preferably, the organic ligand comprises at least one of o-phenanthroline, 2,2-bipyridine, melamine and phenylalanine; further, the organic solvent comprises at least one of dimethyl sulfoxide and ethanol; Preferably, the organic solvent comprises at least one of dimethyl sulfoxide and ethanol; Preferably, in the second solution, the molar ratio of the active metal precursor salt to the organic ligand is 1:5-1:20; Preferably, in the second solution, based on the total volume of the second solution, the molar concentration of the active metal precursor salt does not exceed 0.2 mol·L -1 ; Preferably, in the second solution, the molar concentration of the organic ligand is no more than 4 mol·L -1 .

10. The reforming microchannel reactor according to claim 1, wherein: The reforming microchannel reactor also includes a coolant located inside the heat exchange cavity; the coolant is selected from molten salt; Preferably, the coolant is LiF-NaF-KF molten salt or KCl-MgCl2 molten salt or NaNO3-NaNO2-KNO3 molten salt.

11. The reforming microchannel reactor according to claim 1, wherein: The temperature and flow control device external to the heat exchange chamber is used to regulate the flow of the coolant in the heat exchange chamber, thereby regulating the temperature of the reforming reaction chamber.

12. A solid oxide fuel cell power generation system, the system comprising: A material supply unit for reforming, a deionized water supply unit, an air supply unit, a fuel supply unit, a microchannel reactor reforming synthesis gas unit and a solid oxide fuel cell; the microchannel reactor reforming synthesis gas unit comprises at least one reforming microchannel reactor according to any one of claims 1 to 11; Among them, the connection relationship between the material supply unit for reforming, the deionized water supply unit, the air supply unit, the fuel supply unit, the microchannel reactor reforming synthesis gas production unit and the solid oxide fuel cell can be achieved: the material supply unit for reforming supplies the material for reforming required for the reforming reaction to the microchannel reactor reforming synthesis gas production unit, the deionized water supply unit supplies the water vapor required for the reforming reaction to the microchannel reactor reforming synthesis gas production unit, the fuel supply unit supplies the fuel required for the catalytic combustion reaction to the microchannel reactor reforming synthesis gas production unit, the air supply unit supplies air to the cathode of the solid oxide fuel cell, and the synthesis gas produced by the reforming reaction of the microchannel reactor reforming synthesis gas production unit is supplied to the anode of the solid oxide fuel cell.

13. The solid oxide fuel cell power generation system according to claim 12, wherein: a heat exchange unit, the heat exchange unit comprising a first heat exchanger, a second heat exchanger, a third heat exchanger, a fourth heat exchanger, a fifth heat exchanger and a sixth heat exchanger; The first fluid inlet of the first heat exchanger is connected to the outlet of the supply unit for the material to be reformed, the first fluid outlet of the first heat exchanger is connected to the first fluid inlet of the fourth heat exchanger, and the first fluid outlet of the fourth heat exchanger is connected to the reforming reaction feed port of the microchannel reactor reforming synthesis gas unit; the first fluid inlet of the second heat exchanger is connected to the outlet of the deionized water supply unit, and the first fluid outlet of the second heat exchanger is connected to the reforming reaction feed port of the microchannel reactor reforming synthesis gas unit; the first fluid inlet of the third heat exchanger is connected to the outlet of the air supply unit, the first fluid outlet of the third heat exchanger is connected to the first fluid inlet of the fifth heat exchanger, and the first fluid outlet of the fifth heat exchanger is connected to the cathode air inlet of the solid oxide fuel cell; the sixth heat exchanger The first fluid inlet of the heat exchanger is connected to the outlet of the fuel supply unit, the first fluid outlet of the sixth heat exchanger is connected to the catalytic combustion reaction feed port of the microchannel reactor reforming synthesis gas production unit; the second fluid inlet of the third heat exchanger is connected to the anode tail outlet of the solid oxide fuel cell, the second fluid outlet of the third heat exchanger is connected to the second fluid inlet of the second heat exchanger, and the second fluid outlet of the second heat exchanger is connected to the second fluid inlet of the first heat exchanger; the catalytic combustion reaction discharge port of the microchannel reactor reforming synthesis gas production unit is connected to the second fluid inlet of the fourth heat exchanger, the second fluid outlet of the fourth heat exchanger is connected to the second fluid inlet of the sixth heat exchanger, and the cathode tail outlet of the solid oxide fuel cell is connected to the second fluid inlet of the fifth heat exchanger; Preferably, the second fluid outlet of the first heat exchanger is connected to the second fluid inlet of the sixth heat exchanger; further, a gas-water separator is provided on the connecting pipeline between the second fluid outlet of the first heat exchanger and the second fluid inlet of the sixth heat exchanger; Preferably, the second fluid outlet of the first heat exchanger is connected to the catalytic combustion reaction feed inlet of the microchannel reactor reforming synthesis gas production unit.

14. The solid oxide fuel cell power generation system according to claim 12, wherein: The microchannel reactor reforming synthesis gas production unit comprises at least two reforming microchannel reactors according to any one of claims 1 to 11, and each reforming microchannel reactor is connected in series in sequence, wherein the reforming reaction outlet of the ith reforming microchannel reactor is connected to the reforming reaction feed inlet of the i+1th reforming microchannel reactor, the coolant feed inlet of the ith reforming microchannel reactor is connected to the coolant outlet of the i+1th reforming microchannel reactor, the catalytic combustion reaction feed inlet of the ith reforming microchannel reactor is connected to the catalytic combustion reaction outlet of the i+1th reforming microchannel reactor, and the catalytic combustion reaction outlet of the first reforming microchannel reactor serves as the microchannel reactor reforming synthesis gas production unit. The catalytic combustion reaction discharge port, the catalytic combustion reaction feed port of the last reforming microchannel reactor serves as the catalytic combustion reaction feed port of the microchannel reactor reforming synthesis gas unit, the reforming reaction discharge port of the last reforming microchannel reactor serves as the reforming reaction discharge port of the microchannel reactor reforming synthesis gas unit, the reforming reaction feed port of the first reforming microchannel reactor serves as the reforming reaction feed port of the microchannel reactor reforming synthesis gas unit, the coolant discharge port of the first reforming microchannel reactor serves as the coolant discharge port of the microchannel reactor reforming synthesis gas unit, and the coolant discharge port of the last reforming microchannel reactor serves as the coolant discharge port of the microchannel reactor reforming synthesis gas unit.

15. The solid oxide fuel cell power generation system according to claim 12, wherein: The material supply unit for reforming includes a desulfurizer, the inlet of the desulfurizer is connected to the source of the material to be reformed, and the outlet of the desulfurizer serves as the outlet of the material supply unit for reforming; and / or The deionized water supply unit comprises a water pump, the inlet of the water pump is connected to the deionized water source, and the outlet of the water pump serves as the outlet of the deionized water supply unit; and / or The air supply unit comprises an air compressor, an inlet of the air compressor is connected to an air source, and an outlet of the air compressor serves as an outlet of the air supply unit.

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