Cylindrical multi-layer reforming hydrogen production device and reforming hydrogen production method

Abstract

The present application relates to the technical field of hydrogen production by reforming, in particular to a cylindrical multilayer hydrogen production device by reforming, which comprises an outer cylinder, a middle cylinder, an inner cylinder, a rotating shaft, a combustion system and an electric heater, wherein both ends of the outer cylinder are provided with sealing plates. The middle cylinder is arranged in the outer cylinder, and a combustion chamber is formed between the outer cylinder and the middle cylinder. Fuel gas inlets and tail gas outlets are formed on the sealing plates corresponding to the positions of the combustion chamber. The combustion system is arranged in the combustion chamber. Both ends of the rotating shaft are rotatably installed on the sealing plates. The inner cylinder is fixed on the rotating shaft and arranged in the middle cylinder. A reaction chamber is formed between the inner cylinder and the middle cylinder, and a plurality of separation nets are arranged to separate the reaction chamber into multiple reaction sections. In addition, the present application also relates to a hydrogen production method by reforming. The present application can realize the optimal utilization of the reforming catalyst by layering the reforming catalyst. The rotating reaction chamber can drive the reforming catalyst to rub against each other, which can effectively remove the accumulated carbon on the reforming catalyst. In addition, multiple heating methods can realize the efficient utilization of energy.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of hydrogen production by reforming, in particular to a cylindrical multi-layer hydrogen production by reforming device and a hydrogen production by reforming method. BACKGROUND

[0002] Hydrogen energy plays a key role in the process of changing energy production and consumption patterns and in the process of transforming traditional energy structure into new energy structure due to its high heat value, zero emissions, renewable and wide sources.

[0003] Methane reforming is an important source of hydrogen energy. Methane itself is also a greenhouse gas. Methane reforming can be converted into syngas to produce hydrogen energy, and syngas can be further used for Fischer-Tropsch synthesis of methanol or other organic compounds. Among various utilization methods of methane, the process of methane steam reforming is relatively mature, has a long history and wide application in chemical synthesis field, and is the main way of industrial hydrogen production at present. As the current large-scale application of methane conversion method, methane steam reforming can not only convert methane into syngas for hydrogen production, but also provide abundant raw materials for downstream industrial production.

[0004] Among them, the catalytic reforming reaction occurring in the methane steam reforming reaction chamber is mainly:

[0005]

[0006]

[0007]

[0008] The hydrogen production by methane reforming process generally includes raw material preheating, desulfurization pretreatment, catalytic reforming, CO conversion, hydrogen purification and waste heat recovery and utilization processes, and the core of the device is the methane steam catalytic reforming process. At present, most of the methane steam reforming devices adopt fixed bed reaction chamber, and the catalytic device is relatively simple, but there are problems of high energy consumption and low hydrogen yield.

[0009] Chinese patent CN1616343A discloses a detachable sample plate type hydrogen production reactor. The device belongs to a fixed bed structure, and aims to improve the problems of uneven temperature distribution of the reaction chamber, space of the reaction system and heat transfer resistance by combining multiple different cavities, so as to improve the reaction efficiency and reaction selectivity. The device has compact structure and can meet the needs of small-scale hydrogen production, but the internal space of the reaction chamber is relatively small, the internal structure of the reaction chamber is complex, and the manufacturing and maintenance costs are high.

[0010] The Chinese patent CN112607705A discloses a water vapor methane reforming hydrogen production device and process, which connects a hydrogenation desulfurization device, a water vapor methane reforming hydrogen production reaction chamber, a low-temperature water vapor shift reaction chamber, a separator and a pressure swing adsorption device in sequence, thereby improving the efficiency of the reforming hydrogen production device. SUMMARY

[0011] (One) technical problems to be solved

[0012] In view of the above-mentioned defects and deficiencies of the prior art, the present application provides an energy-saving and efficient cylindrical multi-layer reforming hydrogen production device and reforming hydrogen production method.

[0013] (Two) technical solutions

[0014] In order to achieve the above-mentioned purpose, the cylindrical multi-layer reforming hydrogen production device of the present application comprises:

[0015] An outer cylinder, both ends of which are provided with end plates;

[0016] A middle cylinder, which is arranged in the outer cylinder, the end portions of the middle cylinder are fixed on the end plates, and a combustion chamber is formed between the outer cylinder and the middle cylinder, a fuel gas inlet and a tail gas outlet are formed on the end plate corresponding to the position of the combustion chamber;

[0017] A combustion system, which is arranged in the combustion chamber;

[0018] A rotating shaft, both ends of which are rotatably installed on the end plates;

[0019] An inner cylinder, which is fixed on the rotating shaft and arranged in the middle cylinder;

[0020] An electric heater, which is arranged inside the inner cylinder;

[0021] Wherein, a reaction chamber is formed between the inner cylinder and the middle cylinder, a plurality of annular separation nets are fixed outside the inner cylinder, and the plurality of separation nets are distributed at intervals to separate the reaction chamber into multiple reaction sections; a catalyst inlet is formed on the end plate corresponding to the position of the reaction chamber, a gas inlet is arranged at the top of the reaction chamber, and a gas outlet and a residue outlet are arranged at the bottom of the reaction chamber.

[0022] Optionally, the reaction chamber is divided into a first reaction section and a second reaction section, the rotating shaft comprises a first shaft corresponding to the first reaction section and a second shaft corresponding to the second reaction section, the inner cylinder comprises a first cylinder fixed on the first shaft in an end face sealing manner and a second cylinder fixed on the second shaft in an end face sealing manner, and a coaxial reverse mechanism is arranged between the first shaft and the second shaft.

[0023] Optionally, the outer cylinder, the middle cylinder and the inner cylinder are vertically placed cylinders arranged coaxially.

[0024] Optionally, baffles or irregular protrusions are arranged on the inner wall of the middle cylinder and the outer wall of the inner cylinder.

[0025] Optionally, a plurality of thermocouples are arranged outside the inner cylinder.

[0026] Optionally, the electric heater comprises electric heating wires arranged longitudinally uniformly.

[0027] Optionally, the combustion system adopts a metal fiber surface burner comprising a porous plate, wherein the diameter of the metal fiber in the combustion system is 40-60 μm; and the combustion system is arranged in a ring shape in the combustion cavity and arranged uniformly.

[0028] Optionally, the reaction chamber is filled with a reforming catalyst in each layer of the reaction section, and the reforming catalyst adopts a spherical solid nickel-based reforming catalyst with a diameter of 10-20 mm, which comprises a composite of any one or several of Ni / Al2O3, Ni / CaAl2O4, Ni / CaAl4O7, Ni / Ca3Al2O6 and Ni / CaAl2O4. 12 Al 14 O 33 .

[0029] Optionally, the inner cylinder and the middle cylinder are heat-conducting cylinders with a thickness of 4-6 mm; the outer cylinder is a high-temperature-resistant heat-insulating cylinder with a thickness of 4-6 mm; and the diameter of the rotating shaft is 40-60 mm.

[0030] Further, the application also provides a reforming hydrogen production method based on the cylindrical multi-layer reforming hydrogen production device.

[0031] S1, filling the reaction chamber with a reforming catalyst, starting a driving motor of a rotating shaft, rotating the reaction chamber at a predetermined rotating speed by the rotating shaft, introducing nitrogen into the reaction chamber from an air inlet, and heating the reaction chamber to a predetermined temperature;

[0032] S2, feeding raw gas into the reaction chamber from the gas inlet at a predetermined flow rate, the rotating shaft rotating the reforming catalyst, and the raw gas contacting the reforming catalyst in the reaction chamber;

[0033] S3, under the action of gravity and the mutual collision of the reforming catalyst, the catalytically generated residues and the carbon deposits on the reforming catalyst falling through the separation net to the bottom of the reaction chamber and being discharged from the residue outlet;

[0034] S4, the reforming gas generated in the reaction chamber gathering in the channel at the bottom of the reaction chamber and being discharged from the gas outlet, and the hydrogen and low-value combustible gas being obtained through subsequent water-gas shift and pressure swing adsorption;

[0035] S5, the low-value combustible gas entering the combustion chamber through the fuel gas inlet below the combustion system after being cooled, the energy obtained by igniting the low-value combustible gas by the combustion system being used by the reaction chamber, and the tail gas after combustion being discharged from the tail gas outlet above the combustion system.

[0036] Optionally, in step S1, after the reaction chamber reaches the predetermined temperature, nitrogen-hydrogen mixed gas is fed into the reaction chamber to reduce the reforming catalyst filled in the reaction chamber, and nitrogen is fed into the reaction chamber again to remove the residual hydrogen in the reaction chamber after reduction.

[0037] The hydrogen content in the nitrogen-hydrogen mixed gas used for reducing the reforming catalyst is 10% to 80%.

[0038] Optionally, the predetermined temperature in the reaction chamber is 700 to 900 DEG C, the water-carbon ratio is 1 to 5, and the carbon space velocity is 5000 to 30000 h-1. -1 The predetermined rotating speed of the rotating shaft is 1 to 5 r / min.

[0039] (III) Beneficial effects

[0040] The technical scheme of the present application provides a cylindrical multi-layer reforming hydrogen production device and a reforming hydrogen production method, which saves complex pretreatment equipment and improves the energy utilization efficiency of the device, so that the methane reforming hydrogen production reaction can be carried out efficiently and stably. After the steam and the purified natural gas or biogas are mixed, they enter the reaction chamber, the raw gas is heated to the required reforming temperature in the reaction chamber by electric heating, and then the reforming reaction occurs under the catalytic action of the reforming catalyst, the high-temperature reforming gas is obtained, the high-purity hydrogen and other low-value combustible gas are obtained after subsequent treatment, the separated low-value combustible gas can be fed into the combustion system as fuel to provide energy for the reforming reaction, and the thermal efficiency can be improved.

[0041] Compared with the prior device, the present application can realize optimal utilization of the reforming catalyst by layering the reforming catalyst, can effectively remove the carbon deposition on the reforming catalyst by rotating the reaction chamber to drive the reforming catalyst to rub against each other, and can realize efficient utilization of energy by selecting a plurality of heating modes according to actual needs.

[0042] The device of the present application is optimized in the design of the reaction chamber, the reforming catalyst filling method, and the integrated configuration of the combustion system and the reaction chamber, and has the following beneficial effects:

[0043] (1) The device of the present application adopts a plurality of heating modes, i.e., an electric heater and a combustion system distributed in a ring shape, to form a plurality of annular heat flow distributions, which can ensure uniform heat transfer and sufficient supply of heat required for the reaction; and the outer cylinder is a high-temperature-resistant heat insulation cylinder, which can reduce heat loss.

[0044] (2) The device has two heating modes, i.e., electric heating and combustion heating, which can be selected according to different situations; or both of the two heating modes can be used to achieve a higher heating rate.

[0045] (3) The separated low-value combustible gas can be introduced into the combustion system as fuel to provide energy for the reforming reaction, so that the heat can be recycled, the energy consumption can be reduced, and the thermal efficiency of the reaction chamber can be improved.

[0046] (4) The partitioned loading of different types of reforming catalysts can realize the mutual cooperation of reforming catalysts with different characteristics and the optimal utilization of the catalytic effect of the reforming catalysts.

[0047] (5) During operation, the rotating shaft is frequency-converted to rotate, which can make the reforming catalysts collide with each other and the equipment, can shake off the carbon deposition on the reforming catalysts in time, and can alleviate the deactivation problem of the reforming catalysts caused by carbon deposition.

[0048] (6) Compared with the single-pipe fixed-bed reaction chamber, the reaction chamber involved in the present application has higher thermal efficiency, which is higher than the current actual plant operation process level, and is not only suitable for on-site hydrogenation stations, but also suitable for hydrogenation systems of marine transportation tools in coastal areas.

[0049] (7) The reforming hydrogen production device provided by the application has simple process flow, convenient operation, high reliability and strong adaptability, and helps to realize the functions of modularization and intelligentization of the hydrogen production device matched with the water-gas shift or pressure swing adsorption purification and the like. BRIEF DESCRIPTION OF DRAWINGS

[0050] Figure 1 Figure 1 is a structural schematic diagram of a cylindrical multi-layer reforming hydrogen production device of the application;

[0051] Figure 2 Figure 1 is a structural schematic diagram of a cylindrical multi-layer reforming hydrogen production device of the application; Figure 1 Figure 1 is a structural schematic diagram of a cylindrical multi-layer reforming hydrogen production device of the application;

[0052] Figure 3 Figure 1 is a structural schematic diagram of a cylindrical multi-layer reforming hydrogen production device of the application.

[0053] LEGEND OF THE DRAWINGS

[0054] 1: rotating shaft; 101: first shaft; 102: second shaft; 2: inner cylinder; 3: electric heater; 4: coaxial reversing mechanism; 5: separation net; 6: middle cylinder; 7: reaction chamber; 8: combustion system; 9: outer cylinder; 10: thermocouple; 11: fuel gas inlet; 12: residue outlet; 13: tail gas outlet; 14: catalyst inlet. DETAILED DESCRIPTION

[0055] In order to better explain the application and facilitate understanding, the application is described in detail below through specific embodiments in combination with the drawings.

[0056] It should be noted that all directional indications, such as up, down, left, right, front, back, etc., in the embodiments of the application are only used to explain the relative positional relationship, movement condition, etc. between components in a certain posture (as shown in the drawings), and if the certain posture changes, the directional indications also change accordingly.

[0057] In addition, the description such as "first", "second" and the like in the application is only for the purpose of description, and cannot be understood as indicating or implying the relative importance of the indicated technical features or implicitly indicating the number of the indicated technical features. Therefore, the features limited by "first", "second" can explicitly or implicitly include at least one of the features. In the description of the application, the meaning of "a plurality of" is at least two, such as two, three, etc., unless otherwise specifically limited.

[0058] In the present application, unless otherwise explicitly specified and limited, the terms "connection", "fixation" and the like should be understood in a broad sense, for example, "fixation" can be fixed connection, or detachable connection, or integral; "connection" can be mechanical connection, or electrical connection; can be directly connected, or indirectly connected through intermediate medium, can be internal communication of two elements or interaction relationship between two elements, unless otherwise explicitly limited. For those skilled in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances.

[0059] Referring to Figure 1 and Figure 2 The present application provides a cylindrical multi-layer reforming hydrogen production device, which comprises an outer cylinder 9, a middle cylinder 6, an inner cylinder 2, a rotating shaft 1, a combustion system 8 and an electric heater 3, wherein both ends of the outer cylinder 9 are provided with end plates. The middle cylinder 6 is arranged in the outer cylinder 9, and the end portions of the middle cylinder 6 are fixed to the end plates. The space between the outer cylinder 9 and the middle cylinder 6 is a combustion chamber, and the combustion system 8 is arranged in the combustion chamber. The end plates are provided with a fuel gas inlet 11 and an exhaust gas outlet 13 corresponding to the position of the combustion chamber. The exhaust gas outlet 13 can be connected to a heat exchanger outside the end plate, and the steam generated by the heat exchanger can be provided to the reaction chamber 7 as the raw material for the steam reforming reaction of methane. The heat provided by the heat exchanger can be used for the preheating of the reaction gas. Both ends of the rotating shaft 1 are rotatably installed on the end plates, and the inner cylinder 2 is fixed to the rotating shaft 1 and arranged in the middle cylinder 6, i.e. the inner cylinder 2 is rotatably installed on the end plates through the rotating shaft 1. Specifically, the rotating shaft 1 penetrates through the first end to the end of the outer cylinder 9, and is rotatably supported by a pair of bearings at both ends of the shaft, and is dynamically sealed at the end plate. The inner cylinder 2 is fixed to the rotating shaft 1 and rotates with the rotating shaft 1. Moreover, the electric heater 3 is arranged inside the inner cylinder 2, and a conductive slip ring can be arranged near the bearing of the rotating shaft 1. The power supply line can pass through the conductive slip ring and then pass through the inside of the rotating shaft 1 to connect to the electric heater 3, so as to supply power to the electric heater 3.

[0060] The space between the inner cylinder 2 and the middle cylinder 6 is a reaction chamber 7, and a plurality of annular partition nets 5 are fixed outside the inner cylinder 2. The partition net 5 can be a stainless steel net, the inner side edge of the partition net 5 is fixed on the outer surface of the inner cylinder 2, and the outer side edge is tightly attached to the inner surface of the middle cylinder 6. The plurality of partition nets 5 are distributed at intervals to divide the reaction chamber 7 into a plurality of reaction sections, for example Figure 1The reaction chamber 7 is divided into a first reaction section Z1 located at the upper portion and a second reaction section Z2 located at the lower portion. A catalyst inlet 14 is formed on the sealing plate corresponding to the position of the reaction chamber 7. The top of the reaction chamber 7 is provided with a gas inlet, and the bottom of the reaction chamber 7 is provided with a gas outlet and a residue outlet 12 for discharging the carbon and residue generated during the reaction. Specifically, the gas inlet and the gas outlet can be formed on the sealing plate. Alternatively, the two ends of the rotating shaft 1 near the dynamic sealing structure can be hollow tubes, and small through holes are formed on the tube walls of the hollow tubes as the gas inlet and the gas outlet. The rotating shaft 1 can be a complete shaft, and the middle portion of the rotating shaft 1 is separated from the hollow tubes at the ends by a partition plate to prevent the gas from flowing out of the outer cylinder 9 directly through the hollow tubes. Alternatively, the rotating shaft 1 can only include two coaxially arranged hollow tubes, and one end surface of the hollow tubes is fixed to the corresponding end surface of the inner cylinder 2. At the top of the reaction chamber 7, the hollow tube is in communication with the reaction chamber 7 through the through hole (equivalent to the gas inlet) in the sealing plate, thereby forming a gas inlet channel. At the bottom of the reaction chamber 7, the reaction chamber 7 is in communication with the external environment through the through hole (equivalent to the gas outlet) in the sealing plate and the hollow tube, thereby forming a gas outlet channel, to form a simple gas path for facilitating the discharge of gas. The raw gas and the steam are mixed by the gas mixing valve and then enter the gas inlet, and the gas outlet can be connected to the induced draft fan. The inner diameter of the rotating shaft 1 is 150-250 mm (preferably 200 mm), and the rotating shaft 1 can be preferably a stainless steel tube.

[0061] The reaction chamber 7 can be filled with reforming catalysts in each layer of the reaction section. The reforming catalysts in adjacent reaction sections can be the same or different. The reforming catalysts are spherical solid nickel-based reforming catalysts with a diameter of 10-20 mm (preferably 10 mm, 15 mm or 20 mm). The spherical solid nickel-based reforming catalysts include any one or a composite of Ni / Al2O3, Ni / CaAl2O4, Ni / CaAl4O7, Ni / Ca3Al2O6 and Ni / CaAl2O4. 12 Al 14 O 33 The diameter of the reforming catalysts is greater than the pore size of the partition net 5 supporting the corresponding reforming catalysts.

[0062] When reforming hydrogen, the desulfurized natural gas / methane gas and steam from the steam generator are mixed and preheated, and then introduced into the reaction chamber 7 through the gas inlet, and after being heated to the required temperature in the reaction chamber 7, the steam reforming reaction of methane is carried out to obtain a reforming gas. The high-temperature reforming gas after the reforming reaction enters the low-temperature water gas shift reactor (existing device) to carry out the water gas shift reaction (exothermic reaction, which can continue to provide heat for the steam reforming reaction of methane), and obtain a hydrogen-rich mixed gas. The hydrogen-rich mixed gas obtained after the water gas shift reaction enters the pressure swing adsorption separation system (existing device) for gas separation and purification, and after the pure hydrogen is separated and purified, the low-value combustible gas remaining is sent to the combustion system 8 for combustion to provide energy for the steam reforming reaction of methane.

[0063] The device of the present application adopts multiple heating methods, and the electric heater 3 and the annular combustion system 8 form a multi-layer annular heat flow distribution, which can ensure uniform heat transfer and sufficient supply of heat required for the reaction. Moreover, the device has two heating methods, i.e. electric heating and combustion heating, which can be selected according to different situations; or both heating methods can be used together to achieve a higher heating rate. In addition, the separated low-value combustible gas can be used as fuel to enter the combustion system to provide energy for the reforming reaction, so that the heat can be recycled, the energy consumption is reduced, and the thermal efficiency of the reaction chamber 7 is improved.

[0064] In the above technical solution, the different types of reforming catalysts filled in different sections can realize the mutual cooperation of reforming catalysts with different properties, and realize the best utilization of the catalytic effect of the reforming catalysts. During operation, the rotating shaft 1 can be driven by a variable frequency motor to rotate at a variable frequency, so that the reforming catalysts can collide with the equipment, and the accumulated carbon on the reforming catalysts can be shaken off in time, and the deactivation problem of the reforming catalysts caused by the accumulated carbon can be alleviated.

[0065] Further, in the preferred embodiment, referring to Figure 1 and Figure 3 , the rotating shaft 1 includes a first shaft 101 corresponding to the first reaction section Z1 and a second shaft 102 corresponding to the second reaction section Z2, the inner cylinder 2 includes a first cylinder fixed on the first shaft 101 by end face sealing and a second cylinder fixed on the second shaft 102 by end face sealing, and a coaxial reverse mechanism 4 (see Figure 3), the inner edge of the annular partition net 5 can be fixed to the bottom end of the first shaft 101 and the second shaft 102 respectively. The internal structure and working principle of the coaxial reversing mechanism 4 are both prior art, and the coaxial reversing mechanism 4 can be wrapped by a dynamic sealing shell which can be heat insulated to isolate the heat in the electric heater 3 or the reaction chamber 7. The coaxial reversing mechanism 4 can make the first shaft 101 and the second shaft 102 of the rotating shaft 1 rotate in opposite directions at the same speed, so as to realize the rotation of the first cylinder corresponding to the first reaction section Z1 and the second cylinder corresponding to the second reaction section Z2 in opposite directions, thereby enhancing the vibration mixing effect on the reforming catalyst, enabling the raw gas to fully contact with the reforming catalyst, and reducing the carbon deposition on the reforming catalyst. In addition, the inner wall of the middle cylinder 6 and the outer wall of the inner cylinder 2 can also be spaced apart and provided with baffles or irregular protrusions, and the baffle can be an isosceles trapezoidal stainless steel plate with a thickness of 5 mm, so as to further improve the vibration mixing effect.

[0066] The outer cylinder 9, the middle cylinder 6 and the inner cylinder 2 are preferably vertically placed cylinders, and the outer cylinder 9, the middle cylinder 6 and the inner cylinder 2 are coaxially arranged to ensure stable operation. The inner cylinder 2 and the middle cylinder 6 can be heat-conducting cylinders with a thickness of 4-6 mm (preferably 5 mm) and are made of metal materials mainly including iron-chromium alloy or ceramic materials mainly including alumina. The cylindrical arrangement can form multi-layer annular heat flow distribution to ensure uniform heat transfer and sufficient supply of heat required for reaction. The outer cylinder 9 is a high-temperature-resistant heat-insulating cylinder with a thickness of 4-6 mm (preferably 5 mm) and is mainly made of ceramic fibers to play a heat-insulating role and reduce heat loss. The inner cylinder 2 is provided with a plurality of thermocouples 10 outside to realize independent monitoring of the temperature of each reaction section and can realize accurate temperature control of each section in cooperation with the electric heater 3.

[0067] The electric heater 3 includes uniformly longitudinally arranged electric heating wires and can control the power of the electric heating wires by a temperature controller. The combustion system 8 adopts a metal fiber surface burner containing a porous plate, which can be a metal fiber-porous ceramic medium surface burner in the prior art. The combustion system 8 is made of very fine metal fibers, and the diameter of the metal fibers can be preferably 40-60 μm. The material of the metal fibers mainly includes iron-chromium-aluminum fibers. Referring to Figure 2 , the combustion system 8 is arranged in a ring shape in the combustion chamber, and twelve metal fiber surface burners are uniformly arranged at intervals. The bottom of the combustion chamber is provided with a fuel inlet pipe inserted into the fuel gas inlet 11, and the fuel inlet pipe is connected to the gas inlet section of each metal fiber surface burner. The top of the combustion chamber is provided with a tail gas outlet pipe connected to the tail gas outlet 13. The reaction chamber 7 can be heated by the electric heater 3 and the combustion system 8 alone or together during the reforming process, and the appropriate heating mode can be selected according to different situations; or the two heating modes can be used together to achieve a higher heating rate.

[0068] In addition, in other embodiments, the upper end of the reaction chamber 7 can also be provided with a circular seamless stainless steel hollow tube, which is provided with a plurality of small through holes with a diameter of 2-3 mm and a center distance of 20-30 mm between adjacent holes, which can be used for waste heat recovery after the methane steam reforming reaction.

[0069] Further, the present application also provides a reforming hydrogen production method based on the above-mentioned cylindrical multi-layer reforming hydrogen production device, which comprises the following steps:

[0070] S1, filling the reaction chamber 7 with reforming catalyst, starting the drive motor (preferably a variable frequency motor) of the rotating shaft 1, and rotating the reaction chamber 7 at a predetermined speed under the driving of the rotating shaft 1, and at the same time, introducing high-purity nitrogen gas into the reaction chamber 7 from the gas inlet, and heating the reaction chamber 7 to a predetermined temperature;

[0071] S2, introducing raw gas (for example, methane and water vapor) into the reaction chamber 7 from the gas inlet at a predetermined flow rate, and rotating (preferably variable frequency rotating) the rotating shaft 1 to drive the reforming catalyst to rotate, so that the raw gas is in full contact with the reforming catalyst in the reaction chamber 7;

[0072] S3, under the action of gravity and the mutual collision of the reforming catalyst, the residues produced by catalysis and the accumulated carbon on the reforming catalyst fall through the separation net 5 to the bottom of the reaction chamber 7, and are discharged from the residue outlet 12;

[0073] S4, the reforming gas produced in the reaction chamber 7 is gathered in the channel at the bottom of the reaction chamber 7, and is discharged through the gas outlet, and after subsequent water-gas shift and pressure swing adsorption, high-purity hydrogen and low-value combustible gas are obtained;

[0074] S5, after the low-value combustible gas is cooled, it enters the combustion chamber through the fuel gas inlet 11 below the combustion system 8, and the energy obtained by igniting the low-value combustible gas by the combustion system 8 can be used by the reaction chamber 7, and the tail gas after combustion is discharged from the tail gas outlet 13 above the combustion system 8.

[0075] The raw gas can include methane-rich gas, air, water vapor and nitrogen-hydrogen mixed gas, the components of the reaction gas for the methane steam reforming reaction can include CO2, CO and the like, and the source of the methane can be natural gas, biogas, pyrolysis gas, gasification gas or coke oven gas. In the preferred embodiment, after the reaction chamber 7 reaches the predetermined temperature, the nitrogen-hydrogen mixed gas is introduced to reduce the reforming catalyst loaded in the reaction chamber 7; and after reduction, high-purity nitrogen gas is introduced again to remove the residual hydrogen gas in the reaction chamber 7. The nitrogen-hydrogen mixed gas can be introduced to reduce the catalyst loaded in the reactor before the reforming reaction, so that the active component nickel in the reforming catalyst is reduced from nickel oxide to elemental nickel, and the hydrogen content in the nitrogen-hydrogen mixed gas used for reducing the reforming catalyst is 10% to 80%. In addition, the predetermined temperature in the reaction chamber 7 can be 700 to 900°C, and can be 700°C, 750°C, 800°C, 850°C, 900°C and the like, the water-carbon ratio can be 1 to 5, and the carbon space velocity can be 5000 to 30000h -1 , and the predetermined rotating speed of the rotating shaft 1 is 1 to 5 r / min. The water-carbon ratio refers to the ratio of the total number of water vapor molecules to the total number of carbon atoms in the feed per unit time. The carbon space velocity refers to the carbon flow processed per unit time and per unit volume of catalyst.

[0076] The process flow of the reforming hydrogen production using the cylindrical multi-layer reforming hydrogen production device is described in detail below through specific examples, and the devices used in the examples have basically the same structure.

[0077] Example 1

[0078] The inner diameter of the reaction chamber 7 is 500 mm, the outer diameter is 600 mm, the height is 1600 mm, the inner cylinder 2 between the electric heater 3 and the reaction chamber 7 is made of heat-conducting material with a thickness of 5 mm; the rotating shaft 1 has an inner diameter of 200 mm and is made of stainless steel material with a thickness of 8 mm; the electric heater 3 has a diameter of 490 mm and a height of 1500 mm, and gaps are left between the upper and lower ends of the inner cylinder 2 and the upper and lower sealing plates of the outer cylinder 9 as gas passages to respectively communicate with the gas inlet and the gas outlet; the material of the middle cylinder 6 between the reaction chamber 7 and the combustion system 8 is the same as that of the inner cylinder 2, and the thickness is also 5 mm; the inner diameter of the combustion chamber is 610 mm, the outer diameter is 690 mm, the height is the same as that of the reaction chamber 7, i.e. 1600 mm, and the outer cylinder 9 is made of high-temperature-resistant heat-insulating material with a thickness of 5 mm.

[0079] The desulfurized natural gas and steam generated by the steam generator are mixed and introduced into the reaction chamber 7. The upper separation net 5 is made of a stainless steel net with a pore size of 15 mm. The first reaction section Z1 is filled with 10 L of spherical Ni / CaAl4O7 reforming catalyst (Ni content of 14 wt%) with a diameter of 20 mm. The lower separation net 5 is made of a stainless steel net with a pore size of 8 mm. The second reaction section Z2 is filled with 10 L of spherical NiAl2O3 reforming catalyst (Ni content of 14 wt%) with a diameter of 10 mm. During operation, the second reaction section Z2 can be filled first, and then the first reaction section Z1 can be filled. The rotating shaft 1 rotates at a speed of 3 r / min. The water-carbon ratio is 3, and the carbon space velocity is 10000 h -1 The methane flow in the raw gas is 3333 L / min, and the steam flow is 10000 L / min. After the raw gas is heated to above 700°C, the steam methane reforming reaction occurs, and the reforming gas is obtained. The high-temperature reforming gas obtained after the reforming reaction is subjected to water gas shift and pressure swing adsorption to obtain hydrogen with high purity and residual other gases (low-value combustible gas). The residual other gas after pressure swing adsorption is introduced into the combustion system 8 as fuel gas. The energy generated by the gas combustion simultaneously provides energy for the reaction chamber 7. The tail gas after combustion is discharged through the tail gas outlet 13 at the upper end of the combustion system 8. The methane conversion rate after reforming is 93.7%, and the hydrogen yield is 76.3%.

[0080] Example 2

[0081] Example 2 and Example 1 use the same reaction equipment, the difference is that the composition of the raw gas is changed. The raw gas is changed to purified biogas (gas components are 71% CH4-25% CO2-4% N2), and the reforming reaction is changed from steam methane reforming to steam-methane-dioxide double reforming.

[0082] The first reaction section Z1 is filled with 20 L of spherical Ni / Al2O3 reforming catalyst with a diameter of 20 mm, and the Ni content is 14 wt%. The second reaction section Z2 is filled with 20 L of spherical Ni / CaAl2O4 reforming catalyst with a diameter of 10 mm, and the Ni content is 14 wt%. The temperature of the reaction chamber 7 is controlled to be 700°C-800°C, and the rotating speed of the rotating shaft 1 is 3 r / min. The water-carbon ratio is 1:1, and the carbon space velocity is 6000 h -1 The raw gas is subjected to reforming reaction in the reaction chamber 7 under the action of the reforming catalyst, and hydrogen product is obtained through subsequent processes. In Example 2, the methane conversion rate is 96.3%, and the hydrogen yield is 84.5%, realizing the high-value utilization of methane gas.

[0083] It should be understood that the embodiments of the present application described above are merely intended to illustrate the technical route and features of the present application, and the purpose is to enable those skilled in the art to understand the content of the present application and to implement it, but the present application is not limited to the above specific embodiments. Any changes or modifications made within the scope of the claims of the present application should be covered within the protection scope of the present application.

Claims

1. A cylindrical multilayer reforming hydrogen production device, characterized in that, include: The outer cylinder (9) has sealing plates at both ends; The middle cylinder (6) is disposed inside the outer cylinder (9). The ends of the middle cylinder (6) are all fixed to the sealing plate. The outer cylinder (9) and the middle cylinder (6) form a combustion chamber. The sealing plate is provided with a fuel gas inlet (11) and an exhaust gas outlet (13) at the position corresponding to the combustion chamber. Combustion system (8), wherein the combustion system (8) is disposed within the combustion chamber; A rotating shaft (1) is rotatably mounted on the sealing plate at both ends; Inner cylinder (2), which is fixed on the rotating shaft (1) and disposed inside the middle cylinder (6); An electric heater (3) is arranged inside the inner cylinder (2); The inner cylinder (2) and the middle cylinder (6) are located between the reaction chamber (7). Multiple annular partition nets (5) are fixed outside the inner cylinder (2). The multiple partition nets (5) are spaced apart to divide the reaction chamber (7) into multiple reaction sections. A catalyst inlet (14) is provided on the sealing plate at the position corresponding to the reaction chamber (7). An air inlet is provided at the top of the reaction chamber (7). An air outlet and a residue outlet (12) are provided at the bottom of the reaction chamber (7).

2. The cylindrical multilayer reforming hydrogen production apparatus according to claim 1, characterized in that, The reaction chamber (7) is divided into a first reaction section (Z1) and a second reaction section (Z2). The rotating shaft (1) includes a first shaft (101) corresponding to the first reaction section (Z1) and a second shaft (102) corresponding to the second reaction section (Z2). The inner cylinder (2) includes a first cylinder whose end face is sealed and fixed on the first shaft (101) and a second cylinder whose end face is sealed and fixed on the second shaft (102). A coaxial reversing mechanism (4) is provided between the first shaft (101) and the second shaft (102).

3. The cylindrical multilayer reforming hydrogen production apparatus according to claim 1 or 2, characterized in that, The outer cylinder (9), the middle cylinder (6) and the inner cylinder (2) are all vertically placed cylinders, and the outer cylinder (9), the middle cylinder (6) and the inner cylinder (2) are arranged coaxially; And / or, baffles or irregular protrusions are arranged at intervals on the inner wall of the middle cylinder (6) and the outer wall of the inner cylinder (2).

4. The cylindrical multilayer reforming hydrogen production apparatus according to claim 1 or 2, characterized in that, Multiple thermocouples (10) are provided on the outside of the inner cylinder (2); And / or, the electric heater (3) includes electric heating wires arranged in a uniform longitudinal direction.

5. The cylindrical multilayer reforming hydrogen production apparatus according to claim 1 or 2, characterized in that, The combustion system (8) adopts a metal fiber surface burner with a porous plate, wherein the diameter of the metal fiber in the combustion system (8) is 40-60 μm; the combustion system (8) is arranged in a ring and uniformly in the combustion chamber.

6. The cylindrical multilayer reforming hydrogen production apparatus according to claim 1 or 2, characterized in that, Each reaction section within the reaction chamber (7) can be filled with a reforming catalyst. The reforming catalyst is a spherical solid nickel-based reforming catalyst with a diameter of 10-20 mm. The spherical solid nickel-based reforming catalyst includes Ni / Al2O3, Ni / CaAl2O4, Ni / CaAl4O7, Ni / Ca3Al2O6, and Ni / Ca 12 Al 14 O 33 A complex composed of any one or more of the following.

7. The cylindrical multilayer reforming hydrogen production apparatus according to claim 1 or 2, characterized in that, The inner cylinder (2) and the middle cylinder (6) are both heat-conducting cylinders with a thickness of 4 to 6 mm; the outer cylinder (9) is a high-temperature resistant heat-insulating cylinder with a thickness of 4 to 6 mm; the diameter of the rotating shaft (1) is 40 to 60 mm.

8. A method for producing hydrogen through reforming, said method being implemented based on the cylindrical multilayer reforming hydrogen production apparatus according to any one of claims 1-7, characterized in that, The reforming method for producing hydrogen includes the following steps: S1. The reforming catalyst is loaded into the reaction chamber (7), and the drive motor of the rotating shaft (1) is started. The rotating shaft (1) drives the reaction chamber (7) to rotate at a predetermined speed. Nitrogen gas is introduced into the reaction chamber (7) from the gas inlet, and the reaction chamber (7) is heated to a predetermined temperature at the same time. S2. Raw material gas is introduced into the air inlet at a predetermined flow rate. The rotating shaft (1) rotates, driving the reforming catalyst to rotate. The raw material gas comes into contact with the reforming catalyst in the reaction chamber (7). S3. Under the action of gravity and the collision between the reforming catalyst and the catalyst, the residue produced by the catalyst and the carbon deposits on the reforming catalyst fall through the separator (5) to the bottom of the reaction chamber (7) and are discharged from the residue outlet (12). S4. The reformed gas generated in the reaction chamber (7) gathers in the channel at the bottom of the reaction chamber (7) and is discharged through the gas outlet. After subsequent water-gas conversion and pressure swing adsorption, hydrogen and low-value combustible gas are obtained. S5. After the low-value combustible gas is cooled, it enters the combustion chamber through the fuel gas inlet (11) below the combustion system (8). The energy obtained by the combustion system (8) in igniting the low-value combustible gas can be used by the reaction chamber (7). The exhaust gas after combustion is discharged from the exhaust gas outlet (13) above the combustion system (8).

9. The method for producing hydrogen through reforming according to claim 8, characterized in that, In step S1, after the reaction chamber (7) reaches the predetermined temperature, a nitrogen-hydrogen mixed gas is introduced to reduce the reforming catalyst packed in the reaction chamber (7); after reduction, nitrogen gas is introduced again to remove the residual hydrogen gas in the reaction chamber (7); The nitrogen-hydrogen mixture used in the reduction reforming catalyst has a hydrogen content of 10% to 80%.

10. The method for producing hydrogen through reforming according to claim 8, characterized in that, The predetermined temperature in the reaction chamber (7) is 700–900°C, the water-to-carbon ratio is 1–5, and the carbon space velocity is 5000–30000 h⁻¹. -1 The predetermined rotational speed of the rotating shaft (1) is 1 to 5 r / min.

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