Auto-thermal reforming hydrogen production device and method and solid oxide fuel cell

Abstract

The invention relates to an autothermal reforming hydrogen production device and method and a solid oxide fuel cell, in particular to the technical field of fuel cells, the autothermal reforming hydrogen production device comprises a combustion chamber, a flue gas tube pass connected with the combustion chamber, and a reforming shell pass matched with the flue gas tube pass; the flue gas tube pass comprises a first heat exchange tube pass, a second heat exchange tube pass and a third heat exchange tube pass which are connected in sequence; a reforming area of the reforming shell side is matched with the first heat exchange tube side; the gas-phase raw material preheating area of the reforming shell pass is matched with the second heat exchange tube pass; a liquid-phase raw material preheating area of the reforming shell pass is matched with the third heat exchange tube pass; and the reforming area is provided with a hydrogen-rich gas outlet. According to the device provided by the invention, the hydrogen-rich gas is prepared by heating the reforming raw material in a heat supply mode of partial combustion, and the high-temperature hydrogen-rich gas directly enters the solid oxide fuel cell stack to be heated to the starting temperature and generate power, so that the starting and stopping efficiency of the solid oxide fuel cell is improved.

Description

Technical Field

[0001] The present invention relates to the field of fuel cell technology, and specifically to an autothermal reforming hydrogen production device and method, a solid oxide fuel cell, and especially to an apparatus and method for preparing high-temperature hydrogen-rich gas by partially combusting steam reforming of high-carbon fuel, and a solid oxide fuel cell. Background Art

[0002] At present, the efficient use of hydrogen energy is inseparable from the fuel cell technology that has been continuously developing in recent years. Hydrogen fuel cells have become a portable, clean, and new energy carrier. However, for hydrogen fuel cells, the supply of hydrogen restricts the widespread application and popularization of hydrogen energy and fuel cells.

[0003] Therefore, how to produce hydrogen efficiently, stably and safely is of great significance to the development of the energy field. The current hydrogen production processes mainly include electrochemical processes centered on water electrolysis, thermochemical processes represented by fuel reforming and coal / biomass gasification, and photochemical processes centered on photocatalytic hydrogen production.

[0004] Propane reforming to produce hydrogen is mainly achieved through two methods: steam reforming and partial oxidation reforming.

[0005] For example, CN114534732A discloses a method for preparing hydrogen catalyst by propane steam reforming. The catalyst contains the following components by mass fraction: 5-20% active component and 95-80% oxide carrier; the active component contains Ni with different Ni / In ratios. x In y The carrier is an oxide. The non-toxic nickel-indium intermetallic compound exhibits excellent selectivity and stability in hydrogen production by propane steam reforming due to its unique electronic structure.

[0006] CN1212965C discloses a method for producing a gas mixture containing hydrogen and carbon monoxide and optionally nitrogen, starting from at least one hydrocarbon selected from the following: methane, propane, butane or LPG or natural gas, including partial catalytic oxidation of one or more hydrocarbons at a temperature of 500-1200°C and a pressure of 3-20 bar in the presence of oxygen or an oxygen-containing gas to produce hydrogen and carbon monoxide; recovering the gas mixture and then purifying or separating it by pressure swing adsorption, temperature swing adsorption or permeation to produce hydrogen with a purity of at least 80% and residual gas that can be supplied to a waste heat power generation device.

[0007] However, the propane partial oxidation reforming reaction is an exothermic reaction. The heat released can lead to the formation of hot spots in the catalyst bed, which will bring a series of adverse consequences. For example, the overheating of the local temperature will lead to the sintering and agglomeration of the active elements, resulting in a reduction in the active surface area of ​​the carrier. Moreover, at such high temperatures, hydrocarbon carbon deposition occurs on the surface of the carrier and is eventually covered by the generated coke. In the steam reforming process, water, as a weak oxidant, can react with carbon deposition to gasify and remove coke, which can extend the service life of the catalyst and the operation cycle of the device.

[0008] Therefore, the use of steam reforming to produce hydrogen can regulate the gas produced by reforming, which is beneficial to protecting the stack, reducing the risk of anode carbon deposition, and extending service life. At the same time, solid oxide fuel cells use solid metal oxides as electrolytes, and use a solid sealed structure as a whole, and the energy conversion efficiency can reach 50-65%. This type of battery avoids the problem of electrolyte leakage, and has the advantages of wide fuel adaptability and long life. Its operating temperature is 500-1000℃, and the startup of the solid oxide fuel cell system usually requires auxiliary power heating, and the stack is heated from the outside of the stack by heat conduction to reach the startup temperature, but this method has the disadvantages of low heating efficiency and high energy consumption.

[0009] Therefore, it is crucial to develop new methods for quickly heating and starting the fuel cell stack. In other words, there is an urgent need for a technical solution that uses partial combustion of raw materials to provide heat and steam reforming to produce high-temperature hydrogen-rich gas to directly enable the solid oxide fuel cell stack to generate electricity, thereby ensuring efficient startup of the solid oxide fuel cell. Summary of the invention

[0010] In view of the problems existing in the prior art, the purpose of the present invention is to provide an autothermal reforming hydrogen production device and method, and a solid oxide fuel cell to solve the defects of low startup efficiency and low energy utilization rate of solid oxide fuel cells.

[0011] To achieve this object, the present invention adopts the following technical solutions:

[0012] In a first aspect, the present invention provides an autothermal reforming hydrogen production device, the autothermal reforming hydrogen production device comprising: a combustion chamber, a flue gas tube connected to the combustion chamber, and a reforming shell configured with the flue gas tube;

[0013] The flue gas tube pass includes a first heat exchange tube pass, a second heat exchange tube pass and a third heat exchange tube pass connected in sequence;

[0014] The reforming zone of the reforming shell side cooperates with the first heat exchange tube side;

[0015] The gas phase feed preheating zone of the reforming shell side cooperates with the second heat exchange tube side;

[0016] The liquid phase feedstock preheating zone of the reforming shell side cooperates with the third heat exchange tube side;

[0017] The reforming zone is provided with a hydrogen-rich gas outlet.

[0018] The autothermal reforming hydrogen production device provided by the present invention, through reasonable setting of the device, adopts a partial combustion heating method to heat the reforming raw material to prepare hydrogen-rich fuel gas. The high-temperature hydrogen-rich gas directly enters the solid oxide fuel cell stack to heat it to the starting temperature and generate electricity, thereby improving the start-stop efficiency and energy utilization rate of the solid oxide fuel cell, which is conducive to the compactness of the portable solid oxide fuel cell system, while reducing the heat loss of the stack and shortening the stack startup time.

[0019] As a preferred technical solution of the present invention, the combustion chamber is provided with a fuel inlet and an oxidant inlet;

[0020] Preferably, an oxidant preheating channel is arranged between the oxidant inlet and the combustion chamber;

[0021] Preferably, the combustion-supporting agent preheating channel is connected to the combustion chamber and the hot gas inlet of the fuel cell stack respectively.

[0022] As a preferred technical solution of the present invention, the hydrogen-rich gas outlet is connected to a solid oxide fuel cell system.

[0023] As a preferred technical solution of the present invention, the gas phase raw material preheating zone and the liquid phase raw material preheating zone are both connected to the reforming zone.

[0024] As a preferred technical solution of the present invention, a liquid storage device is provided between the liquid-phase raw material preheating zone and the third heat exchange tube pass.

[0025] As a preferred technical solution of the present invention, at least one heat exchange tube is arranged in the first heat exchange tube pass.

[0026] As a preferred technical solution of the present invention, at least one heat exchange tube is arranged in the second heat exchange tube pass.

[0027] As a preferred technical solution of the present invention, at least one heat exchange tube is arranged in the third heat exchange tube pass.

[0028] In a second aspect, the present invention provides a method for producing hydrogen through autothermal reforming, the method comprising:

[0029] The heat obtained from the combustion of the fuel is used in turn to drive the reforming reaction, preheat the gaseous raw materials for the reforming reaction, and preheat the liquid raw materials for the reforming reaction, after which the flue gas is discharged;

[0030] At the same time, the heat obtained from the combustion is used to preheat the combustion aid, and the preheated combustion aid is burned and fed into the fuel cell stack.

[0031] In a third aspect, the present invention provides a solid oxide fuel cell, wherein the solid oxide fuel cell uses the hydrogen-rich gas obtained from the autothermal reforming hydrogen production device as described in the first aspect to directly start the solid oxide fuel cell stack.

[0032] Compared with the prior art solutions, the present invention has the following beneficial effects:

[0033] (1) The autothermal reforming hydrogen production device provided by the present invention realizes a miniaturized, visualized and compact structural design of reforming hydrogen production by coupling a burner to a reformer. It has a wide fuel adaptability and can be used for reforming hydrogen production from a variety of hydrocarbon fuels such as methane, propane, and liquefied petroleum gas.

[0034] (2) Part of the heat released by combustion in the autothermal reforming hydrogen production device provided by the present invention is utilized in a cascade manner through a reformer, an air preheater, a fuel preheater and a water heater. At the same time, an air channel is designed on the outside of the burner to reduce heat dissipation losses. At the same time, the solid oxide fuel cell system is directly started with high-temperature hydrogen-rich gas to achieve flexible start and stop of the fuel cell stack. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 is an isometric schematic diagram of an autothermal reforming hydrogen production device provided by an embodiment of the present invention;

[0036] Figure 2 It is an isometric side cross-sectional schematic diagram of an autothermal reforming hydrogen production device provided by an embodiment of the present invention;

[0037] Figure 3 This is a temperature distribution diagram during the autothermal reforming hydrogen production process in Example 1 of the present invention.

[0038] In the figure: 10-combustion chamber, 11-fuel inlet, 12-combustion aid inlet, 13-hot gas outlet, 14-combustion chamber window, 15-combustion aid preheating channel, 20-hydrogen-rich gas outlet, 21-reforming zone window, 22-first heat exchange tube pass, 23-reforming zone, 30-gas phase raw material inlet, 31-hot material pipe, 32-second heat exchange tube pass, 33-gas phase raw material preheating zone, 40-liquid phase raw material inlet, 41-liquid storage device, 42-third heat exchange tube pass, 43-liquid phase raw material preheating zone, 50-flue gas outlet.

[0039] The present invention is further described in detail below. However, the following examples are only simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims. DETAILED DESCRIPTION

[0040] To better illustrate the present invention and facilitate understanding of the technical solution of the present invention, typical but non-limiting embodiments of the present invention are as follows:

[0041] This embodiment provides an autothermal reforming hydrogen production device, such as Figure 1 and Figure 2 As shown, the autothermal reforming hydrogen production device comprises: a combustion chamber 10, a flue gas tube connected to the combustion chamber 10, and a reforming shell configured with the flue gas tube;

[0042] The flue gas tube pass includes a first heat exchange tube pass 22, a second heat exchange tube pass 32 and a third heat exchange tube pass 42 connected in sequence;

[0043] The reforming zone 23 of the reforming shell side cooperates with the first heat exchange tube side 22;

[0044] The gas phase feed preheating zone 33 of the reforming shell side cooperates with the second heat exchange tube side 32;

[0045] The liquid phase feed preheating zone 43 of the reforming shell side cooperates with the third heat exchange tube side 42;

[0046] The reforming zone 23 is provided with a hydrogen-rich gas outlet 20 .

[0047] The combustion chamber 10 is provided with a fuel inlet 11 and an oxidant inlet 12 .

[0048] In the present invention, the fuel and the combustion aid fed into the combustion chamber 10 can be distributed by the gas distribution device and then burned, thereby ensuring the completeness of the combustion.

[0049] Wherein, an oxidant preheating channel 15 is arranged between the oxidant inlet 12 and the combustion chamber 10 .

[0050] The combustion agent preheating channel 15 is connected to the combustion chamber 10 and the hot gas inlet of the fuel cell stack respectively.

[0051] In the present invention, the gas preheated by the combustion-supporting agent preheating channel 15 is fed into the hot gas inlet of the fuel cell stack through the hot gas outlet 13 to supply hot gas for the fuel cell stack.

[0052] In the present invention, the reforming zone is filled with a propane reforming hydrogen production catalyst commonly used in the art to ensure the progress of the reforming reaction.

[0053] Wherein, the hydrogen-rich gas outlet 20 is connected to a solid oxide fuel cell system.

[0054] The gas-phase raw material preheating zone 33 and the liquid-phase raw material preheating zone 43 are both connected to the reforming zone 23 .

[0055] In the present invention, the gaseous raw material fed from the gaseous raw material inlet 30 is preheated in the gaseous raw material preheating zone 33 and then fed into the reforming zone 23 through the hot material pipe 31 for reforming reaction.

[0056] Wherein, a liquid storage device 41 is provided between the liquid-phase raw material preheating zone 43 and the third heat exchange tube pass 42 .

[0057] In the present invention, the liquid raw material introduced through the liquid raw material inlet 40 can be directly introduced into the reforming zone 23 or stored in the liquid storage device 41 and then introduced into the reforming zone 23 after being preheated in the liquid raw material preheating zone 43 .

[0058] Among them, at least one heat exchange tube is arranged in the first heat exchange tube pass 22, for example, it can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25 or 30, but is not limited to the listed values, and other values ​​not listed within the range also meet the requirements.

[0059] Among them, at least one heat exchange tube is arranged in the second heat exchange tube pass 32, for example, it can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25 or 30, but is not limited to the listed values, and other values ​​not listed within the range also meet the requirements.

[0060] Among them, at least one heat exchange tube is arranged in the third heat exchange tube pass 42, for example, it can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25 or 30, but is not limited to the listed values, and other values ​​not listed within this range also meet the requirements.

[0061] In the present invention, the combustion chamber 10 and the reforming zone 23 may be optionally provided with windows such as the combustion chamber window 14 and the reforming zone window 21 for observing the progress of the reaction.

[0062] In the present invention, the flue gas duct side and the reforming shell side can be optionally equipped with temperature detection equipment to detect the reaction temperature of each section, and at the same time, the reasonable progress of each section of the reaction in the device is achieved through intelligent control operation equipment such as controllers such as industrial computers. Furthermore, the combustion startup process is intelligently optimized through intelligent algorithms to achieve efficient hydrogen production and efficient start and stop and energy utilization of solid oxide fuel cells.

[0063] In the present invention, the use process of the autothermal reforming hydrogen production device is as follows: fuel such as methane, propane, and liquefied petroleum gas is introduced into the combustion chamber 10 for combustion, and the flue gas generated by the combustion flows through the first heat exchange tube 22, the second heat exchange tube 32, and the third heat exchange tube 42 in sequence and flows out through the flue gas outlet 50. During the process, the flue gas passing through the first heat exchange tube 22 heats the reforming zone 23 so that the reforming process can be carried out, the flue gas passing through the second heat exchange tube 32 heats the reforming gas raw material such as propane in the gas raw material preheating zone 30, and the flue gas passing through the third heat exchange tube 42 heats the reforming liquid raw material such as water in the liquid raw material preheating zone 43. The heated propane and water are transported to the reforming zone 23 through the material pipe for reforming reaction to produce hydrogen, and the resulting hydrogen-rich gas is fed into the solid oxide fuel cell through the hydrogen-rich gas outlet 20.

[0064] Furthermore, this embodiment provides a method for producing hydrogen by autothermal reforming, the method comprising:

[0065] The heat obtained from the combustion of the fuel is used in turn to drive the reforming reaction, preheat the gaseous raw materials for the reforming reaction, and preheat the liquid raw materials for the reforming reaction, after which the flue gas is discharged;

[0066] At the same time, the heat obtained from the combustion is used to preheat the combustion aid, and the preheated combustion aid is burned and fed into the fuel cell stack.

[0067] In the present invention, the catalyst used in the reforming reaction is a commonly used catalyst in the art, such as a 20% Ni / Al2O3 catalyst in terms of mass percentage, wherein Ni is an active component and Al2O3 is a carrier.

[0068] In the present invention, the temperature of the propane after preheating is 125-175°C, and the reforming reaction space velocity is 100-120s -1 .

[0069] In the present invention, the temperature control during the reforming process is achieved by controlling the combustion of the fuel, such as the amount of fuel fed, to control the generation of heat, thereby controlling the temperature of each section in the device and further regulating the reforming process.

[0070] Furthermore, the present invention provides a solid oxide fuel cell, wherein the solid oxide fuel cell uses the hydrogen-rich gas obtained by the aforementioned autothermal reforming hydrogen production device to directly start the solid oxide fuel cell stack.

[0071] Further, in order to illustrate the good reforming effect that can be achieved by the autothermal reforming hydrogen production device provided by the present invention, the following actual example is used for exemplary description, as follows:

[0072] Example 1

[0073] This embodiment provides a process for producing hydrogen through autothermal reforming, using the following apparatus:

[0074] A combustion chamber 10, a flue gas tube connected to the combustion chamber 10, and a reforming shell configured with the flue gas tube;

[0075] The flue gas tube pass includes a first heat exchange tube pass 22, a second heat exchange tube pass 32 and a third heat exchange tube pass 42 connected in sequence;

[0076] The reforming zone 23 of the reforming shell side cooperates with the first heat exchange tube side 22;

[0077] The gas phase feed preheating zone 33 of the reforming shell side cooperates with the second heat exchange tube side 32;

[0078] The liquid phase feed preheating zone 43 of the reforming shell side cooperates with the third heat exchange tube side 42;

[0079] The reforming zone 23 is provided with a hydrogen-rich gas outlet 20 .

[0080] The combustion chamber 10 is provided with a fuel inlet 11 and an oxidant inlet 12 .

[0081] In this embodiment, the fuel and the combustion aid are fed into the combustion chamber 10 and then burned after being distributed by the gas distribution device, thereby ensuring the completeness of the combustion.

[0082] An oxidant preheating channel 15 is arranged between the oxidant inlet 12 and the combustion chamber 10; the oxidant preheating channel 15 is connected to the combustion chamber 10 and the hot gas inlet of the fuel cell stack respectively; wherein the gas preheated by the oxidant preheating channel 15 is fed into the hot gas inlet of the fuel cell stack through the hot gas outlet 13 to supply hot gas for the fuel cell stack;

[0083] The hydrogen-rich gas outlet 20 is connected to a solid oxide fuel cell system;

[0084] The gas-phase raw material preheating zone 33 and the liquid-phase raw material preheating zone 43 are both connected to the reforming zone 23; the gas-phase raw material fed from the gas-phase raw material inlet 30 is preheated in the gas-phase raw material preheating zone 33, and then fed into the reforming zone 23 through the hot material pipe 31 for reforming reaction; a liquid storage device 41 is arranged between the liquid-phase raw material preheating zone 43 and the third heat exchange tube pass 42; the liquid-phase raw material fed from the liquid-phase raw material inlet 40 is preheated in the liquid-phase raw material preheating zone 43, stored in the liquid storage device 41, and then fed into the reforming zone 23.

[0085] The hydrogen production process is as follows: the heat obtained from the combustion of the fuel is used in turn to drive the reforming reaction, preheat the gaseous raw materials for the reforming reaction, and preheat the liquid raw materials for the reforming reaction, and the resulting flue gas is discharged;

[0086] At the same time, the heat obtained from the combustion is used to preheat the combustion aid, and the preheated combustion aid is burned and fed into the fuel cell stack;

[0087] Specifically, steam reforming is used to produce hydrogen without closed insulation (the reforming catalyst is 20% Ni / Al2O3 catalyst, in which Ni is the active component and Al2O3 is the carrier, and the space velocity is 112s -1 , propane flow rate is 1.5L / min, water flow rate is 0.54L / h), the above device is ignited and tested, and the temperature distribution curve of each monitoring point is obtained by monitoring the reformer outlet temperature, the reforming chamber temperature, the air preheating flow channel temperature, the raw material preheating flow channel temperature, the combustion chamber outer wall temperature, the reforming chamber outer wall temperature and the water tank temperature. Figure 3 As shown in the figure, when the propane burner power is 10kW, after 4 hours of long-term operation, the reforming chamber outlet gas temperature is maintained at about 200℃. Continuing to increase the burner power to 13.5kW and 19.6kW, the reforming chamber outlet temperature will continue to rise. The combustion chamber outer wall temperature is about 80℃, compared with the reforming chamber outer wall temperature of about 250℃, indicating that the current air preheating channel effectively reduces the heat dissipation loss of the burner.

[0088] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0089] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0090] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. An autothermal reforming hydrogen production device, characterized in that: The autothermal reforming hydrogen production device comprises: a combustion chamber, a flue gas pipe connected to the combustion chamber, and a reforming shell configured with the flue gas pipe; The flue gas tube pass includes a first heat exchange tube pass, a second heat exchange tube pass and a third heat exchange tube pass connected in sequence; The reforming zone of the reforming shell side cooperates with the first heat exchange tube side; The gas phase feed preheating zone of the reforming shell side cooperates with the second heat exchange tube side; The liquid phase feedstock preheating zone of the reforming shell side cooperates with the third heat exchange tube side; The reforming zone is provided with a hydrogen-rich gas outlet.

2. The autothermal reforming hydrogen production device according to claim 1, characterized in that: The combustion chamber is provided with a fuel inlet and an oxidant inlet; Preferably, an oxidant preheating channel is arranged between the oxidant inlet and the combustion chamber; Preferably, the combustion-supporting agent preheating channel is connected to the combustion chamber and the hot gas inlet of the fuel cell stack respectively.

3. The autothermal reforming hydrogen production device according to claim 1, characterized in that: The hydrogen-rich gas outlet is connected to a solid oxide fuel cell system.

4. The autothermal reforming hydrogen production device according to claim 1, characterized in that: The gas phase raw material preheating zone and the liquid phase raw material preheating zone are both connected to the reforming zone.

5. The autothermal reforming hydrogen production device according to claim 1, characterized in that: A liquid storage device is arranged between the liquid-phase raw material preheating zone and the third heat exchange tube pass.

6. The autothermal reforming hydrogen production device according to claim 1, characterized in that: At least one heat exchange tube is arranged in the first heat exchange tube pass.

7. The autothermal reforming hydrogen production device according to claim 1, characterized in that: At least one heat exchange tube is arranged in the second heat exchange tube pass.

8. The autothermal reforming hydrogen production device according to claim 1, characterized in that: At least one heat exchange tube is arranged in the third heat exchange tube pass.

9. A method for producing hydrogen by autothermal reforming, characterized in that: The autothermal reforming hydrogen production method comprises: The heat obtained from the combustion of the fuel is used in turn to drive the reforming reaction, preheat the gaseous raw materials for the reforming reaction, and preheat the liquid raw materials for the reforming reaction, after which the flue gas is discharged; At the same time, the heat obtained from the combustion is used to preheat the combustion aid, and the preheated combustion aid is burned and fed into the fuel cell stack.

10. A solid oxide fuel cell, characterized in that: The solid oxide fuel cell uses the hydrogen-rich gas obtained from the autothermal reforming hydrogen production device as described in any one of claims 1 to 8 to directly start the solid oxide fuel cell stack.

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