A flat-tube type hydrogen production device for catalytic steam reforming of methane based on a proton membrane reactor

Abstract

The present invention belongs to the technical field of catalytic reaction, and particularly relates to a flat-tube methane steam catalytic reforming hydrogen production device based on a proton membrane reactor, which comprises a reforming reactor main body. A first reaction chamber and a second reaction chamber are arranged inside the reforming reactor main body. A proton membrane reactor is arranged inside the first reaction chamber. The proton membrane reactor comprises a cathode layer, a proton membrane layer, an electrolyte layer and an anode layer. An electrolyte reactor is arranged inside the second reaction chamber. The present invention combines the reforming reactor with proton exchange membrane technology, and the proton membrane reactor is combined between the electrolyte and the cathode in a sandwich form to construct a layer-by-layer mass transfer structure, avoiding the problems of discontinuous reaction separation process, low separation efficiency, low energy conversion efficiency and high energy consumption caused by unreasonable combination of the reforming reactor and the proton membrane reactor, realizing the efficient conversion of the methane steam reforming reaction and the efficient separation of products, having the advantages of high overall energy conversion rate, simple and compact process, etc., and having broad application prospects.

Description

Technical Field

[0001] The invention belongs to the technical field of catalytic reaction, and in particular relates to a flat tube type methane steam catalytic reforming hydrogen production device based on a proton membrane reactor. Background Art

[0002] China is transforming its energy structure from high carbon to low carbon and then to zero carbon. Against this background, energy structure reform and the development of low-carbon renewable energy have become inevitable trends. Compared with traditional energy, hydrogen energy has the advantages of high calorific value, clean combustion products, wide access and renewable. With the increasing demand for clean energy and the rapid development of hydrogen energy research, the global demand for hydrogen energy is getting bigger and bigger. Due to its huge share in global energy consumption, fossil energy will continue to be the main energy source for human survival for a long time. Therefore, the new process of preparing hydrogen and synthesis gas from natural gas has become a frontier field in the discipline of clean energy conversion.

[0003] CN114408865A discloses a chemical chain methane reforming hydrogen production device. Through the design and research of the induction heating temperature control mode, heat transfer / mass transfer timing control and other aspects during the heating process of the integral honeycomb oxygen carrier, compared with the existing fixed bed and fluidized bed processes, the efficient and stable chemical chain methane reforming hydrogen production device has the advantages of fast response speed and no particle abrasion during the reaction process, avoiding the problems of oxygen carrier breakage and reactor abrasion in the traditional fluidized bed reactor. CN103373706A discloses a methane reforming hydrogen production method and device, the main structure of which includes a fluidized reforming reactor, a regenerator and a heat exchanger. The method and device eliminate the reduction device after the catalyst regeneration, simplify the process flow, and save equipment investment. Electrochemical reaction cells have also been reported to be used for methane reforming reactions. CN113832473A discloses a method of passing methane to the anode surface, passing direct current between the cathode and cathode, causing the anode to undergo methane oxidation reaction and generate hydrogen.

[0004] However, there are few reports on combining proton membrane reactors with other electric reaction cells as methane steam reforming reactors. The main reason is that the two have different working conditions and unreasonable combined structures, which will make the reforming separation process discontinuous and the product transfer and collection blocked, leading to low efficiency and low structural strength. In view of this, by combining the proton membrane reactor in the form of a sandwich between the electrolyte and the cathode of the flat tube reformer, a layer-by-layer mass transfer structure is constructed to fully and synergistically play the excellent characteristics of the proton membrane reactor with low energy consumption and high energy conversion efficiency and the flat tube catalytic reformer with large catalytic effective area and high catalytic efficiency, and realize an efficient, near-zero-loss methane steam reforming catalytic process and efficient collection process. Summary of the invention

[0005] In view of the above deficiencies of the prior art, the present invention provides a flat-tube methane steam catalytic reforming hydrogen production device based on a proton membrane reactor, which solves the problems of discontinuous reaction separation process, low separation efficiency, low energy conversion efficiency, and high energy consumption caused by the unreasonable design of the combination method of the existing flat-tube catalytic reformer and the proton exchange membrane reactor.

[0006] To achieve the above object, the technical solution adopted by the present invention is as follows: providing a flat-tube methane steam catalytic reforming hydrogen production device based on a proton membrane reactor, including a reforming reactor main body, and a first reaction chamber and a second reaction chamber are arranged inside the reforming reactor main body;

[0007] On one side of the first reaction chamber, a plurality of reaction gas inlets are arranged, a gas product outlet is arranged between the plurality of reaction gas inlets, and a proton membrane reactor is arranged inside it. The proton membrane reactor includes a cathode layer, a proton membrane layer, an electrolyte layer, and an anode layer arranged in sequence from top to bottom;

[0008] An electrolyte reactor is arranged in the second reaction chamber, a power supply is arranged between the electrolyte reactor and the proton membrane reactor, and the power supply is electrically connected to the cathode layer and the anode layer.

[0009] The beneficial effects of adopting the above technical solution are as follows: Methane and carbon dioxide required for the reforming reaction enter the inside of the first reaction chamber from the reaction gas inlets. As the power supply inside the first reaction chamber is turned on and the temperature rises, the reforming reaction occurs. The hydrogen generated by the reaction then enters the second reaction chamber, and carbon dioxide is discharged from the gas product outlet; By arranging a proton membrane reactor and an electrolyte reactor in two reaction chambers, and combining the proton membrane reactor and the electrochemical reaction cell as a methane steam reforming reactor, the energy conversion efficiency is effectively improved; At the same time, the proton membrane reactor is combined between the electrolyte layer and the cathode layer in the form of a sandwich to construct a layer-by-layer mass transfer structure inside the reforming reactor, overcoming the problems of discontinuous reaction separation process, low separation efficiency, low energy conversion efficiency, and high energy consumption caused by the unreasonable design of the combination method of the reforming reactor and the proton membrane reactor, realizing the efficient conversion of methane steam reforming reaction and the efficient separation of products, and the conversion process is simple and compact, effectively improving the overall energy conversion efficiency of the reforming reactor.

[0010] Further, a hydrogen channel is arranged above the proton membrane reactor, and an anode layer is arranged above the hydrogen channel.

[0011] The beneficial effects of adopting the above technical solution are as follows: During the reforming reaction process, the hydrogen generated can be separated from the inner side of the proton membrane to the hydrogen channel under the action of the proton membrane, current, and voltage, and is transported to the second reaction chamber through the hydrogen channel.

[0012] Further, the electrolyte reactor includes a cathode layer, an electrolyte layer, and an anode layer arranged in sequence from top to bottom.

[0013] Furthermore, a hydrogen channel is provided below the anode layer.

[0014] The beneficial effects of adopting the above technical solution are as follows: By applying voltage and current to the electrolyte layer, hydrogen ions enter the second reaction chamber from the first reaction chamber. The hydrogen ions pass through the anode layer and the electrolyte layer, generate hydrogen gas at the cathode layer, and are discharged through the hydrogen channel for unified collection.

[0015] Furthermore, the materials of both the anode layer and the cathode layer are Ni-based composite oxides.

[0016] The beneficial effects of adopting the above technical solution are as follows: Ni-based composite oxides have high activity, selectivity, and stability, and are inexpensive.

[0017] Furthermore, the material of the electrolyte layer is Ba-based oxide.

[0018] A method for using a flat-tube type methane steam catalytic reforming hydrogen production device based on a proton membrane reactor includes the following steps:

[0019] S1: After preheating and uniformly mixing the reaction gases methane and carbon dioxide, they enter the interior of the first reaction chamber of the reforming reactor main body from the reaction gas inlet;

[0020] S2: Raise the temperature inside the reforming reactor main body, and carry out a reforming reaction in the first reaction chamber to produce hydrogen and carbon dioxide;

[0021] S3: Turn on the power supply, apply voltage and current to the electrolyte layer, and hydrogen is transported from the first reaction chamber to the second reaction chamber through the proton membrane to obtain separated and compressed hydrogen;

[0022] S4: The carbon dioxide generated by the reforming reaction is discharged from the gas product outlet.

[0023] The beneficial effects of adopting the above usage method are as follows: By combining the reforming reactor with the proton membrane reactor, the reforming reaction of methane and water occurs in the proton membrane reactor. The proton membrane reactor is composed of a reactor and a proton membrane, making the reaction device more compact and greatly improving the degree of reaction progress and the raw material conversion rate; at the same time, the proton membrane reactor can also extend the residence time, expand the reaction temperature and pressure range, and shorten the length of the reactor main body; in addition, in the first reaction chamber, during the reaction process, hydrogen will be transported along the hydrogen channel to the second reaction chamber as the reaction proceeds, thereby promoting the reaction to move towards the product direction, achieving the purpose of improving the conversion rate and the product yield.

[0024] In summary, the beneficial effects of the flat-tube type methane steam catalytic reforming hydrogen production device based on a proton membrane reactor provided by the present invention are as follows:

[0025] (1) The present invention combines a proton membrane reactor and an electrolyte reactor as a methane steam reforming reactor, which not only simplifies the reaction device and operation, but also ensures the continuity of the reforming and separation processes, avoiding problems such as low conversion efficiency and low structural strength caused by blocked product transfer and collection.

[0026] (2) The catalytic reforming reaction of the present invention combines a thermochemical process and an electrochemical process. The process is simple and compact, and can achieve the purpose of efficient conversion of the methane steam reforming reaction and efficient separation of products, greatly improving the overall energy conversion efficiency of the device and having good application prospects.

[0027] (3) The proton membrane reactor in the present invention is combined between the electrolyte and the cathode in the form of a sandwich, forming a layer-by-layer mass transfer structure inside the reforming reactor, overcoming the problems of discontinuous reaction separation process, low separation efficiency, low energy conversion efficiency and high energy consumption caused by the combination of a flat tube catalytic reformer and a proton membrane reactor. Brief Description of the Drawings

[0028] Figure 1 is a schematic structural diagram of the present invention;

[0029] Figure 2 is a partially enlarged schematic structural diagram of the proton membrane reactor.

[0030] Among them, 1, main body of the reforming reactor; 2, first reaction chamber; 3, reaction gas inlet; 4, gas product outlet; 5, proton membrane reactor; 6, cathode layer; 7, proton membrane layer; 8, anode layer; 9, hydrogen channel; 10, second reaction chamber; 11, electrolyte reactor; 12, electrolyte layer; 13, power supply. Detailed Embodiments

[0031] The following describes the detailed embodiments of the present invention to facilitate those skilled in the art of the present technology to understand the present invention. However, it should be clear that the present invention is not limited to the scope of the detailed embodiments. For those of ordinary skill in the art of the present technology, as long as various changes are within the spirit and scope of the present invention defined and determined by the appended claims, these changes are obvious, and all inventions made using the concept of the present invention are within the scope of protection.

[0032] Such as Figure 1As shown in the figure, the flat-tube methane steam catalytic reforming hydrogen production device based on a proton membrane reactor provided by the present invention includes a reforming reactor main body 1, and a first reaction chamber 2 and a second reaction chamber 10 are arranged inside the reforming reactor main body 1; several reaction gas inlets 3 are arranged on one side of the first reaction chamber 2, a gas product outlet 4 is arranged between the several reaction gas inlets 3, and a proton membrane reactor 5 is arranged inside it. The proton membrane reactor 5 includes a cathode layer 6, a proton membrane layer 7, an electrolyte layer 12, and an anode layer 8 arranged in sequence from top to bottom; an electrolyte reactor 11 is arranged in the second reaction chamber 10, a power supply 13 is arranged between the electrolyte reactor 11 and the proton membrane reactor 5, and the power supply 13 is electrically connected to the cathode layer 6 and the anode layer 8; during use, the power supply 13 is used to provide the voltage required for the catalytic reforming reaction. Methane and water required for the reforming reaction enter the inside of the first reaction chamber 2 from the reaction gas inlets 3. As the power supply 13 inside the first reaction chamber 2 is turned on and the temperature rises, the reforming reaction occurs, and the hydrogen generated by the reaction subsequently enters the second reaction chamber 10, and carbon dioxide is discharged from the gas product outlet 4; by arranging the proton membrane reactor 5 and the electrolyte reactor 11 in the two reaction chambers, and combining the proton membrane reactor 5 and the electrolytic reactor 11 as a methane steam reforming reactor, the device structure and operation process are simplified, and the energy conversion efficiency is effectively improved.

[0033] In this embodiment, as Figure 2 shown, the proton membrane reactor 5 includes a cathode layer 6, a proton membrane layer 7, an electrolyte layer 12, and a tubular anode layer 8 arranged in sequence from top to bottom, and a hydrogen channel 9 is arranged above the proton membrane reactor 5, and the anode layer 8 is arranged above the hydrogen channel 9; the proton membrane reactor 5 is combined between the electrolyte layer 12 and the cathode layer 6 in the form of a sandwich to construct a layer-by-layer mass transfer structure inside the reforming reactor, overcoming the problems of discontinuous reaction separation process, low separation efficiency, low energy conversion efficiency, and high energy consumption caused by the unreasonable design of the combination method of the reforming reactor and the proton membrane reactor 5, realizing the efficient conversion of the methane steam reforming reaction and the efficient separation of products, and the conversion process is simple and compact, effectively improving the overall energy conversion efficiency of the reforming reactor.

[0034] In this embodiment, the materials of the anode layer 8 and the cathode layer 6 are both Ni-based composite oxides; the Ni-based composite oxides have high activity, selectivity and stability, and low price.

[0035] As Figure 1As shown in the figure, the electrolyte reactor 11 includes a cathode layer 6, an electrolyte layer 12, and an anode layer 8 arranged sequentially from top to bottom. A hydrogen channel 9 is provided below the anode layer 8, and the electrolyte layer 12 is made of Ba-based oxide. During use, the power supply 13 is turned on, a voltage and current are applied to the electrolyte layer 12, hydrogen ions enter the second reaction chamber 10 from the first reaction chamber 2, pass through the anode layer 8 and the electrolyte layer 12, generate hydrogen gas at the cathode layer 6, and are discharged through the hydrogen channel 9 for unified collection.

[0036] The method of using the flat-tube methane steam catalytic reforming hydrogen production device based on a proton membrane reactor provided by an embodiment of the present invention includes the following steps:

[0037] S1: After preheating and uniformly mixing the reaction gases methane and carbon dioxide, they enter the interior of the first reaction chamber 2 of the reforming reactor main body 1 from the reaction gas inlet 3;

[0038] S2: Raise the temperature inside the reforming reactor main body 1, and a reforming reaction occurs in the first reaction chamber 2 to produce hydrogen and carbon dioxide;

[0039] S3: Turn on the power supply 13, apply a voltage and current to the electrolyte layer 12, and hydrogen is transmitted from the first reaction chamber 2 to the second reaction chamber 10 through the proton membrane to obtain separated and compressed hydrogen;

[0040] S4: The carbon dioxide generated by the reforming reaction is discharged from the gas product outlet 4.

[0041] The method of use in this embodiment combines a thermochemical process and an electrochemical process, which can balance the net endothermic chemical reaction with the heat generated by the galvanic operation of the electrochemical cell, achieve the purpose of efficient conversion of the methane steam reforming reaction and efficient separation of products, greatly improve the overall energy conversion efficiency of the device, and has good application prospects.

[0042] In summary, the flat-tube methane steam catalytic reforming hydrogen production device based on a proton membrane reactor provided by the present invention combines the proton membrane reactor 5 and the electrolyte reactor 11 as the methane steam reforming reactor, which not only simplifies the reaction device and operation, but also ensures the continuity of the reforming and separation process. Moreover, the proton membrane reactor 5 is combined between the electrolyte and the cathode in the form of a sandwich, forming a layer-by-layer mass transfer structure inside the reforming reactor, overcoming the problems of discontinuous reaction separation process, low separation efficiency, low energy conversion efficiency, and high energy consumption caused by the combination of the flat-tube catalytic reformer and the proton membrane reactor 5.

Claims

1. A flat-tube type hydrogen production device for catalytic steam reforming of methane based on a proton membrane reactor, characterized in that: It includes a reforming reactor main body (1), and a first reaction chamber (2) and a second reaction chamber (10) are arranged inside the reforming reactor main body (1); hydrogen is unidirectionally transmitted between the first reaction chamber (2) and the second reaction chamber (10) through a proton membrane layer (7). On one side of the first reaction chamber (2), a plurality of reaction gas inlets (3) are arranged. A gas product outlet (4) is arranged between the plurality of reaction gas inlets (3). A proton membrane reactor (5) is arranged inside it. The proton membrane reactor (5) is embedded in the reforming reactor main body in the form of a sandwich. The proton membrane reactor (5) includes a cathode layer (6), a proton membrane layer (7), an electrolyte layer (12), and an anode layer (8) arranged in sequence from top to bottom. An electrolyte reactor (11) is arranged in the second reaction chamber (10). A power supply (13) is arranged between the electrolyte reactor (11) and the proton membrane reactor (5). The power supply (13) is electrically connected to the cathode layer (6) and the anode layer (8). A hydrogen channel (9) is arranged above the proton membrane reactor (5), and the anode layer (8) is arranged above the hydrogen channel (9). The electrolyte reactor (11) includes a cathode layer (6), an electrolyte layer (12), and an anode layer (8) arranged in sequence from top to bottom. A hydrogen channel (9) is arranged below the anode layer (8).

2. The flat-tube methane steam catalytic reforming hydrogen production device based on a proton membrane reactor according to claim 1, characterized in that: The materials of the anode layer (8) and the cathode layer (6) are both Ni-based composite oxides.

3. The flat-tube type hydrogen production device for catalytic steam reforming of methane based on a proton membrane reactor according to claim 1, characterized in that: The material of the electrolyte layer (12) is Ba-based oxide.

4. The usage method of the flat tube type methane steam catalytic reforming hydrogen production device based on a proton membrane reactor according to any one of claims 1-3, characterized in that, It includes the following steps: S1: After preheating and mixing the reaction gases methane and carbon dioxide evenly, they enter the inside of the first reaction chamber (2) of the reforming reactor main body (1) from the reaction gas inlet (3). S2: Raise the temperature inside the reforming reactor main body (1), and a reforming reaction occurs in the first reaction chamber (2) to generate hydrogen and carbon dioxide. S3: Turn on the power supply (13), apply voltage and current to the electrolyte layer (12), and hydrogen is transmitted from the first reaction chamber (2) to the second reaction chamber (10) through the proton membrane to obtain separated and compressed hydrogen. S4: The carbon dioxide generated by the reforming reaction is discharged from the gas product outlet (4).

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