Self-heating revolving bed chemical chain steam reforming hydrogen production reactor and use method thereof

Abstract

The invention relates to a self-heating rotating bed chemical looping steam reforming hydrogen production reactor and a using method, the reactor comprises a rotating bed reactor support, a rotating bed reactor, an upper inlet and outlet chamber and a lower inlet and outlet chamber, the upper inlet and outlet chamber is fixedly installed on the rotating bed reactor support, and the lower inlet and outlet chamber is fixedly installed on the rotating bed reactor support. The rotating bed reactor is rotationally connected between the upper inlet-outlet chamber and the lower inlet-outlet chamber; the upper inlet / outlet chamber and the lower inlet / outlet chamber are respectively provided with six pipe orifices which respectively correspond to gas inlets / outlets of the fuel reactor, the steam reforming reactor, the air reactor and the three scavenging transition areas, and the interiors of the upper inlet / outlet chamber and the lower inlet / outlet chamber are divided into six equal areas through a plurality of partition plates; the space in a cavity of the rotating bed reactor is divided into six areas, including a fuel reactor, a steam reforming reactor, an air reactor and three scavenging transition areas arranged at intervals. According to the invention, the continuous hydrogen production process with zero pollutant discharge and self-sufficient reaction heat is realized.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical looping steam reforming for hydrogen production from natural gas, and more particularly, to a self-heating rotary bed chemical looping steam reforming hydrogen production reactor and its usage method. Background Art

[0002] Hydrogen energy is a clean and efficient secondary energy source, and has an important strategic position in the process of low-carbon and green transformation of China's energy structure. However, the current core bottleneck restricting the large-scale application of hydrogen energy lies in the significant technical barriers in the construction of distributed hydrogen production and refueling stations. In the existing technology, the traditional fossil fuel hydrogen production process adopts a distributed layout of multiple reactors. The differences in the dynamic response characteristics of each reaction unit lead to difficulties in the coordinated control of the system, low utilization rate of reaction heat, and high overall energy consumption of the system. The direct participation of air in the high-temperature combustion zone will lead to the generation of NO x pollutants, which fundamentally contradicts the clean characteristics of hydrogen energy application, and at the same time poses additional equipment requirements for the tail gas separation and purification of the system. In addition, the material transfer between multiple reactors needs to rely on a complex pipeline system, which will further increase the floor area of the equipment and the construction cost of hydrogen production equipment. Therefore, developing a new type of hydrogen production reactor with self-heating operation, modular integration, and zero pollutant emissions has become the key technical direction to break through the bottleneck in the construction of distributed hydrogen production and refueling integrated stations. Summary of the Invention

[0003] In view of the above-mentioned technical problems, a self-heating rotary bed chemical looping steam reforming hydrogen production reactor and its usage method are provided. By using chemical looping steam reforming technology and multi-reactor integration, problems such as high energy consumption, pollutant emissions, coordinated control of multiple reactors, and low equipment space utilization rate in the existing hydrogen production process are solved, and an efficient and clean continuous hydrogen production process is realized.

[0004] The technical means adopted by the present invention are as follows:

[0005] A self-heating rotary bed chemical looping steam reforming hydrogen production reactor, comprising a rotary bed reactor support, a rotary bed reactor, an upper inlet and outlet chamber, and a lower inlet and outlet chamber. The upper inlet and outlet chamber is arranged above the rotary bed reactor, the lower inlet and outlet chamber is arranged below the rotary bed reactor. The upper inlet and outlet chamber is fixedly installed on the rotary bed reactor support, the lower inlet and outlet chamber is fixedly installed on the rotary bed reactor support, and the rotary bed reactor is rotatably connected between the upper inlet and outlet chamber and the lower inlet and outlet chamber;

[0006] Six nozzles are respectively arranged on the upper inlet / outlet chamber and the lower inlet / outlet chamber, corresponding to the gas inlets and outlets of the fuel reactor, the steam reforming reactor, the air reactor and the three purge transition zones. The interior of the upper inlet / outlet chamber and the lower inlet / outlet chamber is divided into six equal parts by a number of partition plates. The space inside the rotating bed reactor cavity is divided into six regions, including a fuel reactor, a steam reforming reactor, an air reactor and three purge transition zones arranged at intervals.

[0007] Further, the rotating bed reactor support includes a frame structure composed of a number of columns and crossbeams. The crossbeams include a top crossbeam, a middle support beam and a bottom crossbeam. The bottoms of the columns are fixed to the ground through the bottom crossbeam. The top crossbeam is connected to the flange of the upper inlet / outlet chamber, and the middle support beam is connected to the flange of the lower inlet / outlet chamber.

[0008] Further, a heat insulation shell is sleeved outside the rotating bed reactor housing.

[0009] Further, the rotating bed reactor is rotated through a worm and worm gear mechanism. Specifically, its power source is a motor arranged on the rotating bed reactor support. A worm is arranged at the output end of the motor, and a helical gear is arranged on the outer wall of the rotating bed reactor.

[0010] Further, a guide shaft is arranged at the center of the rotating bed reactor. The guide shaft is connected to each partition plate, and guide bearings are respectively arranged at the upper and lower ends of the guide shaft.

[0011] The present invention also discloses a use method of the above self-heating type rotating bed chemical looping steam reforming hydrogen production reactor, including the following steps:

[0012] Step 1, using a high-temperature carbon dioxide purge working medium to purge each reactor region in the rotating bed reactor cavity to remove the original impurity gas in the reactor;

[0013] Step 2, starting the transmission device to drive the rotating bed to rotate periodically to equalize the temperature field in the reactor. At the same time, the temperature in the reactor is monitored in real time. When the temperature in the reactor reaches the lowest reaction temperature, stop purging the reactor region;

[0014] Step 3, starting the feeding device, natural gas enters the fuel reactor through the fuel reactor inlet. Carbon dioxide and water vapor are generated and discharged from the fuel reactor through the fuel reactor outlet. After a set reaction residence time, the oxygen carriers on the wall surface of the microchannels in the rotating bed are all reduced, and the channels where they are located are transferred to the first purge transition zone and enter the steam reforming reactor after being purged by carbon dioxide;

[0015] Step 4: Steam enters the steam reforming reactor through the steam reforming reactor inlet. The generated hydrogen gas leaves the reactor through the steam reforming reactor outlet. After a set reaction residence time, the partial oxidation reaction of the oxygen carrier on the wall of the rotating bed microchannel is complete, and the channel where it is located enters the second purge transition zone. After being purged with carbon dioxide, it enters the air reactor;

[0016] Step 5: Air enters the air reactor through the air reactor inlet. After a set reaction residence time, the oxygen carrier on the wall of the rotating bed microchannel is completely oxidized, and the channel where it is located enters the third purge transition zone. After being purged with carbon dioxide, it enters the next chemical looping reaction cycle.

[0017] Compared with the prior art, the present invention has the following advantages:

[0018] 1. Based on the technical principle of chemical looping steam reforming of natural gas to produce hydrogen, the present invention utilizes the relatively low oxidation temperature of 600 - 800 °C in the chemical looping reaction, avoiding the generation of NO during the reaction of fuel and air in the fuel reactor under high temperature environment in the traditional hydrogen production process; x ;

[0019] 2. Through the rotating bed structure integrated with multiple reactors, the fuel reactor, air reactor, and steam reforming reactor that are dispersed in the traditional chemical looping hydrogen production process are innovatively integrated into a single rotating bed reactor. High-purity H2 and CO2 can be efficiently produced without additional separation equipment, realizing the coordinated control of multiple reactors, and significantly reducing the system volume compared with the traditional process flow;

[0020] 3. By using honeycomb ceramics with a microporous structure as the rotating bed and utilizing the independence between the pores and the reasonable sector area partition design, the sufficiency and stability of the reaction in each reactor are ensured, realizing the process of periodic rotation continuous hydrogen production;

[0021] 4. By making the gas flow directions in the fuel reactor and the air reactor opposite to each other, a countercurrent chemical looping reaction is formed, enabling the reaction heat in the air reactor to be effectively transferred to the fuel reactor, and realizing the self-heating chemical looping steam reforming hydrogen production process of the rotating bed reactor. Description of the Drawings

[0022] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0023] Figure 1It is a schematic diagram of the overall structure of the rotating bed reactor in the present invention.

[0024] Figure 2 It is a schematic diagram of the cavity structure of the upper inlet and outlet chamber in the present invention.

[0025] Figure 3 It is a schematic diagram of the cavity structure of the reactor region in the present invention.

[0026] Figure 4 It is a schematic diagram of the cavity structure of the lower inlet and outlet chamber in the present invention.

[0027] Figure 5 It is a schematic diagram of the transmission rotor structure in the present invention.

[0028] Figure 6 It is a schematic diagram of the microporous honeycomb ceramic structure in the present invention.

[0029] In the figure: 1. Rotating bed reactor support; 2. Heat preservation shell; 3. Motor; 4. Rotating bed reactor housing; 5. Upper inlet and outlet chamber; 6. Lower inlet and outlet chamber; 7. Guide shaft; 8. Fuel reactor gas outlet; 9. Steam reforming reactor gas inlet; 10. Air reactor gas inlet; 11. Sweep gas transition zone gas outlet; 12. Fuel reactor gas inlet; 13. Steam reforming reactor gas outlet; 14. Air reactor gas outlet; 15. Sweep gas transition zone gas inlet; 16. End sealing device; 17. Reaction zone partition; 18. Upper layer fixed bed heat preservation layer; 19. Middle layer rotating bed reaction layer; 20. Lower layer fixed bed heat preservation layer; 21. Circumferential sealing device; 22. Support bearing; 23. Guide bearing; 24. Fuel reactor; 25. Steam reforming reactor; 26. Air reactor; 27. Sweep gas transition zone; 29. Radial sealing piece. Detailed implementation manners

[0030] It should be noted that, without conflict, the embodiments in the present invention and the features in the embodiments can be combined with each other. The present invention will be described in detail below with reference to the drawings and in combination with the embodiments.

[0031] To make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and in no way restrictive of the present invention and its application or use. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0032] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments of the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they specify the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0033] Unless otherwise specifically stated, the relative arrangements of components and steps, numerical expressions, and numerical values set forth in these embodiments do not limit the scope of the present invention. At the same time, it should be clear that, for the sake of convenience of description, the dimensions of the various parts shown in the drawings are not drawn in actual proportional relationships. Technologies, methods, and devices known to those of ordinary skill in the relevant art may not be discussed in detail, but where appropriate, such technologies, methods, and devices should be regarded as part of the specification. In all the examples shown and discussed herein, any specific value should be construed as merely exemplary and not as a limitation. Therefore, other examples of the exemplary embodiments may have different values. It should be noted that like reference numerals and letters denote like items in the following drawings, and thus, once an item is defined in one drawing, further discussion thereof is not required in subsequent drawings.

[0034] In the description of the present invention, it should be understood that the orientation or positional relationships indicated by orientation words such as "front, rear, upper, lower, left, right", "lateral, vertical, perpendicular, horizontal", and "top, bottom" are generally based on the orientation or positional relationships shown in the drawings, and are only for the convenience of describing the present invention and simplifying the description. Without contrary description, these orientation words do not indicate and imply that the device or element referred to must have a specific orientation or be constructed and operated in a specific orientation, and thus should not be construed as limiting the protection scope of the present invention: the orientation words "inside, outside" refer to the inside and outside relative to the contour of each component itself.

[0035] For ease of description, spatially relative terms such as "above", "above", "on the upper surface of", "above", etc. may be used here to describe the spatial positional relationship between a device or feature and other devices or features as shown in the figure. It should be understood that spatially relative terms are intended to include different orientations of the device in use or operation in addition to the orientation described in the figure. For example, if the device in the accompanying drawings is inverted, the device described as "above other devices or structures" or "above other devices or structures" will be positioned as "below other devices or structures" or "below their position devices or structures". Thus, the exemplary term "above" can include both "above" and "below". The device can also be positioned in other different ways (rotated 90 degrees or in other orientations), and the spatially relative descriptions used here are interpreted accordingly.

[0036] In addition, it should be noted that the use of terms such as "first" and "second" to limit components is only for the convenience of distinguishing the corresponding components. If not otherwise stated, the above terms have no special meaning and therefore cannot be understood as limiting the scope of protection of the present invention.

[0037] like Figures 1 to 6 As shown, an embodiment of the present invention discloses a self-heating rotating bed chemical looping steam reforming hydrogen production reactor, comprising a rotating bed reactor support 1, a rotating bed reactor, an upper inlet and outlet chamber 5 and a lower inlet and outlet chamber 6, wherein the upper inlet and outlet chamber 5 is arranged at the upper part of the rotating bed reactor, and the lower inlet and outlet chamber 6 is arranged at the lower part of the rotating bed reactor, the upper inlet and outlet chamber 5 is fixedly mounted on the rotating bed reactor support 1, and the lower inlet and outlet chamber 6 is fixedly mounted on the rotating bed reactor support 1, and the rotating bed reactor is rotatably connected between the upper inlet and outlet chamber 5 and the lower inlet and outlet chamber 6;

[0038] The upper inlet and outlet chamber 5 and the lower inlet and outlet chamber 6 are each provided with six pipe openings, which correspond to the gas inlets and outlets of the fuel reactor 24, the steam reforming reactor 25, the air reactor 26 and the three purge transition zones 27 respectively. The interior of the upper inlet and outlet chamber 5 and the lower inlet and outlet chamber 6 is divided into six equal areas by a plurality of partition plates 17. The rotating bed reactor includes a rotating bed reactor shell 4, in which a rotating bed reactor cavity is arranged. The space in the rotating bed reactor cavity is divided into six areas, including the fuel reactor 24, the steam reforming reactor 25, the air reactor 26 and the three purge transition zones 27 arranged at intervals.

[0039] The rotating bed reactor enables the oxygen carrier to undergo a chemical chain cycle reaction in each reaction area through the periodic and continuous rotation of the rotating bed, thereby realizing a continuous hydrogen production process from natural gas.

[0040] In this embodiment, the main body of the rotating bed reactor housing 4 is a cylinder. According to specific arrangements, extension sections with gradually decreasing diameters can be provided at the upper and lower ends to connect with the upper inlet / outlet chamber 5 and the lower inlet / outlet chamber 6. Or the cylinder can be directly connected to the upper inlet / outlet chamber 5 and the lower inlet / outlet chamber 6 with variable diameter structures. The attached drawings of this embodiment will be introduced in the latter implementation manner.

[0041] In this embodiment, a fuel reactor gas outlet 8, a steam reforming reactor gas inlet 9, an air reactor gas inlet 10, and three scavenging transition zone gas outlets 11 are provided on the upper inlet / outlet chamber 5, and a fuel reactor gas inlet 12, a steam reforming reactor gas outlet 13, an air reactor gas outlet 14, and three scavenging transition zone gas inlets 15 are provided on the lower inlet / outlet chamber 6.

[0042] The rotating bed reactor support 1 includes a frame structure composed of several columns and crossbeams. The crossbeams include a top crossbeam, a middle support beam, and a bottom crossbeam. The bottom of the columns is fixed to the ground through the bottom crossbeam. The top crossbeam is connected to the flange of the upper inlet / outlet chamber 5, and the middle support beam is connected to the flange of the lower inlet / outlet chamber 6. Most of the weight of the rotating bed reactor is borne and fixed through the top crossbeam and the middle support beam.

[0043] A heat preservation outer shell 2 is sleeved outside the rotating bed reactor housing to achieve heat insulation between the reactor and the external environment. In this embodiment, the heat preservation outer shell covers the outside of the rotating bed reactor housing and is supported by four auxiliary columns. The heat preservation outer shell of the rotating bed reactor is sleeved on the outer shell of the rotating bed reactor to ensure no heat exchange between the rotating bed reactor and the external environment and reduce heat loss.

[0044] As an alternative implementation manner, the rotating bed reactor is rotated through a worm and worm gear mechanism. Specifically, its power source is a motor 3 provided on the rotating bed reactor support. A worm is provided at the output end of the motor, and a helical gear is provided on the outer wall of the rotating bed reactor. The motor 3 is fixed to the structural crossbeam in the middle of the support through bolt connections. At the same time, to ensure the structural strength, the middle structural crossbeam and the main structural column are provided with reinforcing ribs to strengthen the bending and torsional resistance of the joints.

[0045] As a preferred implementation manner, in this embodiment, as Figure 5As shown, the rotating bed reactor includes an upper fixed bed insulation layer 18, a middle rotating bed reaction layer 19, and a lower fixed bed insulation layer 20, which is a disc-shaped structure composed of honeycomb-structured ceramic blocks in three layers. Both the upper and lower layers are fixed and can be directly connected to the reactor shell to maintain fixation. The statement "the outer wall of the rotating bed reactor is provided with helical gears" specifically means that the outer wall of the middle rotating bed reaction layer 19 is provided with helical gears. The motor 3 drives the worm to act, driving the middle rotating bed reaction layer 19 to rotate. The motor is a servo motor, which is convenient for precisely controlling the rotation angle of the rotating bed. The motor drives the worm to rotate periodically according to a preset law, thereby driving the seamless switching connection of each reactor area in the middle rotating bed reaction layer 19 in the reactor, realizing the chemical looping reaction of the oxygen carrier on the rotating bed and the continuous and efficient hydrogen production process. In this embodiment, the main part that rotates in the "rotating bed" is the middle rotating bed reaction layer; as other alternative embodiments, more or fewer layers are divided, as long as any layer including the layer where the middle rotating bed reaction layer is located can complete the rotating function of the rotating bed, it shall fall within the protection scope of the present invention.

[0046] The six partition plates that divide the interior of the device into six equal parts in this embodiment are the main plate structures. As other alternative embodiments, according to the actual situation, relatively complex and uniformly distributed partition intervals can be set inside each partition plate of the six-equal-partition plate in the middle rotating bed reaction layer 19, such as Figure 5 shown. By calculating the reaction rates of each reactor area and reasonably designing the area of the fan-shaped reactor area, the sufficiency and efficiency of the chemical looping reaction of the oxygen carrier in each reactor area can be ensured.

[0047] At the position where the partition plates are connected, that is, at the center of the middle, there is a cylindrical central bearing part. A guide shaft 7 is provided at the center of the rotating bed reactor. The guide shaft passes through the central bearing part. The upper and lower ends of the guide shaft respectively pass through the upper inlet and outlet chamber 5 and the lower inlet and outlet chamber 6 and are provided with guide bearings 23 at corresponding positions. A support bearing 22 is provided at the lower part of the rotating bed reactor shell to bear its axial load.

[0048] The central bearing part is a variable-diameter structure or the guide shaft is a variable-diameter structure, so that the guide shaft is connected to the central bearing part of the middle rotating bed reaction layer 19 and has a rotational relationship with the upper fixed bed insulation layer 18 and the lower fixed bed insulation layer 20. Specifically, a number of bearings are provided at the connection positions of the upper fixed bed insulation layer 18, the lower fixed bed insulation layer 20 and the guide shaft. When the guide shaft is a variable-diameter structure, the diameter of the middle part in the vertical direction is larger than the diameters of the upper and lower ends; when the central bearing part is a variable-diameter structure, the diameter of the central hole of the central bearing part is slightly smaller than the diameters of the upper and lower ends.

[0049] The top of the guiding shaft protrudes a certain distance above the top end of the upper inlet and outlet chamber 5. The guiding shaft at this position can be marked with angular dimensions for external monitoring during rotation.

[0050] End sealing devices 16 are provided at the connections between the upper and lower parts of the housing and the upper inlet and outlet chamber 5 and the lower inlet and outlet chamber 6 respectively to prevent gas leakage at the reactor ends and gas mixing between different reactor regions. Grooves for installing the end sealing devices 16 are provided on the inner walls of the upper inlet and outlet chamber 5 and the lower inlet and outlet chamber 6, or the end sealing devices are directly installed between the upper inlet and outlet chamber 5 and the upper fixed bed insulation layer 18, and between the lower inlet and outlet chamber 6 and the lower fixed bed insulation layer 20. The end sealing device can be installed in the groove. The structure of the end sealing device includes an outer sealing ring, an inner ring adapted to the guiding shaft, a dividing part adapted to the partition plates of each partition, and a central through-hole part for installing / passing through the guiding bearing 23.

[0051] According to the actual application situation, the honeycomb ceramic blocks with three layers of microchannels are assembled with the guiding rotating shaft 7 by a plurality of support bearings 22 and guiding bearings 23 distributed axially, thereby realizing the bearing of axial loads and the limitation of radial displacement during the working process in the reactor cavity.

[0052] As Figure 6 shown, the reaction chamber is filled with honeycomb ceramic blocks having a large number of microchannel structures. Each microchannel penetrates up and down, and the gas flow between the channels is independent of each other. It is usually composed of inert materials such as SiC and SiN with good thermal inertia and thermal conductivity. The upper fixed bed insulation layer 18 and the lower fixed bed insulation layer 20 in the reaction chamber are only filled with the inert honeycomb ceramic blocks. The middle rotating bed reaction layer 19 in the reaction chamber is filled with the inert honeycomb ceramic blocks, and a catalyst coating with Al2O3 and MgAl2O4 as carriers and metal oxide oxygen carriers (Me x O y ) distributed on the carriers is further coated on the inner wall surface of its channels. The oxygen carriers usually adopt transition metal oxides (such as NiO, Fe2O3, CuO, MnO2) or composite metal oxides (such as perovskite-type La 1-x Sr x FeO3). The above materials can be reasonably selected according to production requirements, and this invention patent does not specifically limit this.

[0053] In this embodiment, the honeycomb ceramic block with a three-layer microchannel structure is assembled with the guiding rotating shaft 7 by means of axially distributed support bearings 22 and three guiding bearings 23. A guiding shaft 7 is arranged at the center of the rotating bed reactor. The upper and lower ends of the guiding shaft pass through the upper inlet and outlet chamber 5 and the lower inlet and outlet chamber 6 respectively, and guiding bearings 23 are arranged at adjacent positions to ensure the coaxiality of each layer structure on the shaft. A support bearing 22 is arranged at the connection between the middle rotating bed reaction layer 19 and the lower fixed bed heat preservation layer 20, and a guiding bearing 23 is arranged at the connection between the middle rotating bed reaction layer 19 and the upper fixed bed heat preservation layer 18. The two ensure the coaxial relative rotation of the middle rotating bed reaction layer 19 with the upper fixed bed heat preservation layer 18 and the lower fixed bed heat preservation layer 20, and at the same time realize the bearing of the axial load and the limitation of the radial displacement during the operation of the rotating bed.

[0054] End sealing devices 16 are arranged at the connections between the upper and lower parts of the shell and the inlet and outlet chambers to prevent gas leakage at the ends of the reactor and gas mixing between different reactor regions. Grooves for installing the end sealing devices 16 are opened at the connections between the upper and lower fixed bed heat preservation layers and the upper and lower inlet and outlet chambers. The end sealing devices are installed in the grooves. Their structure includes: an external sealing ring and an internal sealing ring arranged inside the sealing ring and adapted to the guiding shaft to prevent gas leakage, and a dividing part adapted to each partition board for preventing gas mixing between different regions of the reactor.

[0055] Circumferential sealing devices 21 are arranged at the connections between the middle rotating bed and the upper and lower fixed beds. Their structure includes: an annular baffle on the outer ring of the rotating bed and an annular groove on the outer ring of the fixed bed adapted thereto. Flame-retardant and heat-resistant grease is filled in the groove to prevent gas leakage at the ends when the rotating bed and the fixed bed rotate relative to each other.

[0056] Flexible radial sealing sheets 29 are arranged along the radial direction of the rotating bed and are closely attached to the ends of the reaction area partition boards of the fixed bed to reduce the radial clearance leakage between different reactor regions during the relative rotation of the rotating bed and the fixed bed and prevent gas mixing between different reaction zones. To ensure the sealing performance, the sealing sheets are replaced regularly after a period of production.

[0057] In addition, in the present invention, carbon dioxide is used as the scavenging working medium, which can not only scavenge the miscellaneous gas in the microchannel area of the rotating bed, but also remove the carbon deposition phenomenon generated due to incomplete oxidation of natural gas in the channel, reduce the temperature fluctuation in the reactor and avoid sintering of the oxygen carrier catalyst, effectively extending the circulation service life of the oxygen carrier.

[0058] The chemical looping reaction process carried out by the middle rotating bed reaction layer 19 in the reactor during actual operation includes:

[0059] 1. The oxidation process of natural gas in the fuel reactor:

[0060] Under the action of a catalyst and at a high temperature of 600 - 800 °C, the following chemical reactions mainly occur in the fuel reactor:

[0061]

[0062] This reaction is an endothermic reaction, and the required heat is provided by the heat released from the reaction in the air reactor through heat transfer by the honeycomb ceramic structure and assisted by the carbon dioxide scavenging working fluid. Natural gas enters the fuel reactor 24 from the fuel reactor inlet 12 in the lower inlet and outlet chamber 6 and reacts with the oxygen carrier. The generated carbon dioxide and water vapor leave the reactor through the fuel reactor outlet 8 in the upper inlet and outlet chamber 5. At the same time, the region where the reduced oxygen carrier is located is transferred to the carbon dioxide scavenging transition zone 27, and after scavenging, it enters the steam reforming reactor 25.

[0063] 2. The water vapor reforming process for hydrogen production in the steam reforming reactor:

[0064] Under the action of a catalyst and at a high temperature of 700 - 900 °C, the following chemical reactions mainly occur in the steam reforming reactor:

[0065]

[0066] This reaction is a slightly exothermic reaction. Water vapor enters the steam reforming reactor 25 from the steam reforming reactor inlet 9 in the upper inlet and outlet chamber 5 and contacts and undergoes a partial oxidation reaction with the reduced oxygen carrier. The generated hydrogen leaves the reactor through the steam reforming reactor outlet 13 in the lower inlet and outlet chamber 6. At the same time, the region where the partially oxidized oxygen carrier is located is transferred to the second carbon dioxide scavenging zone transition 27, and after scavenging, it enters the air reactor 26;

[0067] 3. The oxygen carrier oxidation process in the air reactor:

[0068] Under the action of a catalyst and at a high temperature of 600 - 900 °C, the following chemical reactions mainly occur in the air reactor:

[0069]

[0070] This reaction is an exothermic reaction, and the heat released by the reaction is used for the endothermic reaction in the fuel reactor and for heating the scavenging. Air enters the air reactor 26 from the air reactor inlet 10 in the upper inlet and outlet chamber 5 and contacts and undergoes an oxidation reaction with the partially oxidized oxygen carrier. The remaining high-temperature mixture of oxygen and nitrogen after the reaction leaves the reactor through the air reactor outlet 14 in the lower inlet and outlet chamber 6. At the same time, the region where the re-oxidized oxygen carrier is located is transferred to the third carbon dioxide scavenging zone transition 27, and after scavenging, it enters the next reaction cycle.

[0071] 4. The partial oxidation process of carbon deposition in the scavenging transition zone:

[0072] Under the action of a catalyst and a high temperature of 600 - 800 °C, the following chemical reactions mainly occur in the scavenging transition zone:

[0073]

[0074] This reaction is an endothermic reaction. Due to less carbon deposition, the heat load of the reaction is relatively low. The heat of reaction is supplied by the heat released from the air reactor through heat transfer in the honeycomb ceramic structure. Carbon dioxide enters the scavenging transition zone 27 from the scavenging transition zone inlet 15 in the lower inlet and outlet chamber 6 and reacts with the carbon particles on the inner wall of the microchannels to remove carbon deposition. The generated carbon monoxide and excess scavenging gas leave the reactor through the scavenging transition zone outlet 11 in the lower inlet and outlet chamber 6.

[0075] The present invention also discloses a method for using the above autothermal rotating bed chemical looping steam reforming hydrogen production reactor, which includes the following steps:

[0076] Step 1: Use high-temperature carbon dioxide scavenging working medium to scavenge each reactor area in the rotating bed reactor cavity to remove the original impurity gases in the reactor;

[0077] Step 2: Start the transmission device to drive the rotating bed to rotate periodically to make the temperature field in the reactor uniform. At the same time, by real-time monitoring the gas outlet temperature of each reactor, specifically, monitoring the gas outlet temperature of each reactor to reflect the temperature in the reactor; when the temperature in the reactor reaches the lowest reaction temperature, stop scavenging the reactor area;

[0078] Step 3: Start the feeding device. Natural gas enters the fuel reactor through the fuel reactor inlet. Carbon dioxide and water vapor are generated and discharged from the fuel reactor through the fuel reactor outlet. After a set reaction residence time, the oxygen carriers on the microchannel walls of the rotating bed are completely reduced, and the channels where they are located are transferred to the first scavenging transition zone and enter the steam reforming reactor after being scavenged by carbon dioxide;

[0079] Step 4: Water vapor enters the steam reforming reactor through the steam reforming reactor inlet. The generated hydrogen leaves the reactor through the steam reforming reactor outlet. After a set reaction residence time, the partial oxidation reaction of the oxygen carriers on the microchannel walls of the rotating bed is complete, and the channels where they are located are transferred to the second scavenging transition zone and enter the air reactor after being scavenged by carbon dioxide;

[0080] Step 5: Air enters the air reactor through the air reactor inlet. After a set reaction residence time, the oxygen carriers on the microchannel walls of the rotating bed are completely oxidized, and the channels where they are located are transferred to the third scavenging transition zone and enter the next chemical looping reaction cycle after being scavenged by carbon dioxide.

[0081] The present invention utilizes an integrated rotating bed structure to solve the problems of difficult coordinated control of multiple reactors, high energy consumption, and large equipment volume, and realizes a continuous hydrogen production process with zero pollutant emissions and self-sufficient reaction heat, which is applicable to the construction of small distributed hydrogen production stations.

[0082] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some or all of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A self-heating rotary bed chemical-looping steam reforming hydrogen production reactor, characterized in that It includes a rotating bed reactor support, a rotating bed reactor, an upper inlet and outlet chamber, and a lower inlet and outlet chamber. The upper inlet and outlet chamber is arranged at the upper part of the rotating bed reactor, and the lower inlet and outlet chamber is arranged at the lower part of the rotating bed reactor. The upper inlet and outlet chamber is fixedly installed on the rotating bed reactor support, and the lower inlet and outlet chamber is fixedly installed on the rotating bed reactor support. The rotating bed reactor is rotatably connected between the upper inlet and outlet chamber and the lower inlet and outlet chamber; Six nozzles are respectively provided on the upper inlet and outlet chamber and the lower inlet and outlet chamber, corresponding to the gas inlets and outlets of the fuel reactor, the steam reforming reactor, the air reactor, and three scavenging transition zones. The interior of the upper inlet and outlet chamber and the lower inlet and outlet chamber is divided into six equal parts by a number of partition plates. The space inside the rotating bed reactor cavity is divided into six regions, including a fuel reactor, a steam reforming reactor, an air reactor, and three scavenging transition zones arranged at intervals.

2. The autothermal rotating bed chemical looping steam reforming hydrogen production reactor according to claim 1, wherein The rotating bed reactor support includes a frame structure composed of a number of columns and crossbeams. The crossbeams include a top crossbeam, a middle support beam, and a bottom crossbeam. The bottom of the columns is fixed to the ground through the bottom crossbeam. The top crossbeam is connected to the flange of the upper inlet and outlet chamber, and the middle support beam is connected to the flange of the lower inlet and outlet chamber.

3. The autothermal rotating bed chemical-looping steam reforming hydrogen production reactor according to claim 1, characterized in that, A heat preservation outer shell is sleeved outside the shell of the rotating bed reactor.

4. The autothermal rotary bed chemical looping steam reforming hydrogen production reactor according to claim 1, wherein, The rotation of the rotating bed reactor is realized through a worm and worm gear mechanism. Specifically, its power source is a motor arranged on the rotating bed reactor support. A worm is provided at the output end of the motor, and a helical gear is arranged on the outer wall of the rotating bed reactor.

5. The autothermal rotating bed chemical-looping steam reforming hydrogen production reactor according to claim 1, characterized in that, A guiding shaft is arranged at the center of the rotating bed reactor. The guiding shaft is connected to each partition plate, and guiding bearings are respectively arranged at the upper and lower ends of the guiding shaft.

6. A method for using a self-heating rotary bed chemical-looping steam reforming hydrogen production reactor, characterized in that, It includes the following steps: Step 1: Use high-temperature carbon dioxide scavenging working medium to scavenge each reactor area in the cavity of the rotating bed reactor to remove the original impurity gas in the reactor; Step 2: Start the transmission device to drive the rotating bed to rotate periodically to equalize the temperature field in the reactor. At the same time, monitor the temperature in the reactor in real time. When the temperature in the reactor reaches the lowest reaction temperature, stop scavenging the reactor area; Step 3: Start the feeding device. Natural gas enters the fuel reactor through the fuel reactor inlet. Carbon dioxide and water vapor are generated and discharged from the reactor through the fuel reactor outlet. After a set reaction residence time, all the oxygen carriers on the wall of the microchannel of the rotating bed are reduced. The channel where it is located is transferred to the first scavenging transition zone and enters the steam reforming reactor after being scavenged by carbon dioxide; Step 4: Water vapor enters the steam reforming reactor through the steam reforming reactor inlet. The generated hydrogen leaves the reactor through the steam reforming reactor outlet. After a set reaction residence time, the partial oxidation reaction of the oxygen carrier on the wall of the microchannel of the rotating bed is complete. The channel where it is located is transferred to the second scavenging transition zone and enters the air reactor after being scavenged by carbon dioxide; Step 5: Air enters the air reactor through the air reactor inlet. After a set reaction residence time, the oxygen carrier on the wall of the microchannel of the rotating bed is completely oxidized. The channel where it is located is transferred to the third scavenging transition zone and enters the next chemical looping reaction cycle after being scavenged by carbon dioxide.

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