Catalyst continuous cycle regeneration methane catalytic cracking hydrogen production device and hydrogen production system

Abstract

The present invention belongs to the technical field of methane catalytic cracking hydrogen production, and specifically relates to a methane catalytic cracking hydrogen production device and a hydrogen production system with continuous catalyst regeneration in a cycle. The hydrogen production device includes a methane catalytic cracking reactor, a steam reforming regeneration reactor and a screw conveyor. The bottom of the methane catalytic cracking reactor is connected to the steam reforming regeneration reactor through a screw conveyor. The interior of the steam reforming regeneration reactor is provided with a steam distributor and the top is connected to the top of the methane catalytic cracking reactor. As the catalytic cracking reaction proceeds, the deactivated catalyst settles to the bottom of the methane catalytic cracking reactor and is transported to the steam reforming regeneration reactor by the screw conveyor. The steam swept upward by the steam distributor contacts the deactivated catalyst, regenerates it and re-enters the catalytic cracking reactor, completing the continuous cycle process of catalysis-deactivation-regeneration-catalysis; by regenerating the deactivated catalyst with water vapor, the safety hazard caused by the entry of oxygen is avoided.

Description

Technical Field

[0001] The present invention belongs to the technical field of methane catalytic cracking hydrogen production, and in particular relates to a methane catalytic cracking hydrogen production device with continuous catalyst cycle regeneration and a hydrogen production system. Background Art

[0002] Catalytic cracking of methane is currently the most commonly used method for hydrogen production in industry. The process is mild, energy-efficient, and produces high-purity hydrogen, eliminating the need for complex gas separation. However, solid carbon, a byproduct of the catalytic cracking process, easily adheres to the catalyst, coating the active sites and deactivating them. This process requires frequent catalyst replacement, resulting in low production efficiency. Addressing the recycling and regeneration of the catalyst is a current research hotspot.

[0003] Prior art CN104998654A discloses a nickel-based catalyst, its preparation method, and a method for catalytic cracking of methane to produce hydrogen. The method is characterized by including a settler, a regenerator, a regeneration inclined tube, and a waiting inclined tube in addition to the reactor. Deactivated catalyst and hydrogen enter the settler through a discharge pipe at the top of the reactor, where the deactivated catalyst settles and enters the regenerator. An oxygen source is introduced into the regenerator to regenerate the catalyst, which then enters the reactor through the regeneration inclined tube. This device enables efficient catalytic cracking of methane while preventing catalyst deactivation due to carbon deposition, reducing the frequency of catalyst replacement and improving production efficiency.

[0004] However, in the prior art, after deactivation, the catalyst is completely discharged through the discharge pipe at the top of the reactor, leaving no catalyst in the reactor. This means that the reaction-regeneration process is a batch process, resulting in low reactor time utilization. Furthermore, catalyst regeneration involves oxidation of the byproduct carbon with oxygen. Since methane and hydrogen, two flammable and explosive gases, are present in the device, the introduction of oxygen poses a safety hazard. Summary of the Invention

[0005] The purpose of the present invention is to provide a methane catalytic cracking hydrogen production device and a hydrogen production system with continuous catalyst recycling and regeneration, so as to solve the technical problem in the prior art that after the catalyst is deactivated, it is completely discharged from the discharge pipe at the top of the reactor. At this time, there is no catalyst in the reactor, that is, the reaction-regeneration process is an intermittent process, and the reactor time utilization rate is low.

[0006] In order to solve the above technical problems, the present invention provides a catalyst continuous cycle regeneration methane catalytic cracking hydrogen production device, comprising: a methane catalytic cracking reactor, a steam reforming regeneration reactor and a screw conveyor; wherein

[0007] The methane catalytic cracking reactor is provided with a gas production port at the top, a catalyst feeding port at the upper part, a methane distributor at the lower part, and a screw conveyor at the bottom;

[0008] The top of the steam reforming regeneration reactor is connected to the upper part of the methane catalytic cracking reactor, the lower part is connected to the screw conveyor, and the bottom is provided with a steam distributor;

[0009] The screw conveyor is used to convey the deactivated catalyst dropped on the bottom of the methane catalytic cracking reactor to the steam reforming regeneration reactor.

[0010] In one embodiment of the present application, the methane catalytic cracking reactor includes a large-diameter tube and a small-diameter tube;

[0011] The top of the large diameter tube is a gas production port, and the side wall is connected to the catalyst feeding port and the top of the steam reforming regeneration reactor;

[0012] The methane distributor is arranged in the small-diameter tube, and the bottom is connected to the screw conveyor.

[0013] In one embodiment of the present application, the inner diameter ratio of the large diameter tube to the small diameter tube is 1.2-3.2.

[0014] In one embodiment of the present application, the ratio of the inner diameter of the small-diameter tube to the inner diameter of the steam reforming regeneration reactor is 0.6-1.8.

[0015] In one embodiment of the present application, the methane distributor and the water vapor distributor are both bowl-shaped distributors;

[0016] The bowl-shaped distributor comprises a bowl body and a bowl cover; the bowl body is hollow inside and an air inlet is provided at the bottom; and the bowl cover is provided with a plurality of air outlets.

[0017] In one embodiment of the present application, a filter is provided on the bowl cover.

[0018] In one embodiment of the present application, the bowl body is hemispherical.

[0019] In one embodiment of the present application, the ratio of the outer diameter of the bowl-shaped distributor to the inner diameter of the small-diameter tube is 0.4-0.8.

[0020] Accordingly, the present invention also provides a hydrogen production system, comprising:

[0021] A methane storage tank, a heater, a catalyst continuous cycle regeneration methane catalytic cracking hydrogen production device as described above, a condenser, a bag-type collector, a solid hydrogen storage device, and a heat exchanger are connected in sequence; wherein

[0022] The gas output from the methane storage tank is heated by the heat exchanger and then enters the heater, and the gas produced by the catalyst continuous cycle regeneration methane catalytic cracking hydrogen production device is heated by the heat exchanger and then enters the condenser.

[0023] The beneficial effects of the present invention are as follows: the catalyst continuous cycle regeneration methane catalytic cracking hydrogen production device of the present invention includes a methane catalytic cracking reactor, a steam reforming regeneration reactor and a screw conveyor, the bottom of the methane catalytic cracking reactor is connected to the steam reforming regeneration reactor through the screw conveyor, the interior of the steam reforming regeneration reactor is provided with a steam distributor and the top is connected to the top of the methane catalytic cracking reactor. As the catalytic cracking reaction proceeds, the deactivated catalyst settles to the bottom of the methane catalytic cracking reactor and is transported to the steam reforming regeneration reactor by the screw conveyor. The steam swept upward by the steam distributor contacts the deactivated catalyst, regenerates it and re-enters the catalytic cracking reactor, completing the continuous cycle process of catalysis-deactivation-regeneration-catalysis. In addition, by regenerating the deactivated catalyst with water vapor, the safety hazard caused by the entry of oxygen is avoided.

[0024] Other features and advantages of the present invention will be described in the following description, and in part will become apparent from the description, or understood by practicing the present invention. The purpose and other advantages of the present invention are realized and obtained by the structures particularly pointed out in the description and the drawings.

[0025] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, preferred embodiments are given below and described in detail with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the specific embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0027] Figure 1 Schematic diagram of the methane catalytic cracking hydrogen production device with continuous cyclic regeneration of the catalyst of the present invention;

[0028] Figure 2 is a side view of a bowl-shaped distributor of the present invention;

[0029] Figure 3 1 is a top view of the bowl cover of the bowl-shaped distributor of the present invention;

[0030] Figure 4 Schematic diagram of the hydrogen production system of the present invention.

[0031] In the picture:

[0032] Methane catalytic cracking reactor 1, large diameter tube 11, gas production port 111, small diameter tube 12, catalyst feeding port 13, methane distributor 14, steam reforming regeneration reactor 2, steam distributor 21, screw conveyor 3, bowl-shaped distributor 4, bowl body 41, air inlet 411, bowl cover 42, air outlet 421;

[0033] Methane storage tank 100 , heater 200 , catalyst continuous cycle regeneration methane catalytic cracking hydrogen production device 300 , condenser 400 , bag collector 500 , solid hydrogen storage 600 , and heat exchanger 700 . DETAILED DESCRIPTION

[0034] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0035] The catalyst in the methane catalytic cracking hydrogen production process can be a metal catalyst, including but not limited to Cu / Al catalyst, Fe / Al2O3 catalyst, Cu / Al2O3 catalyst, Ni / Cu / Al catalyst, and Ni / Mg catalyst.

[0036] The reaction process of steam reforming regeneration is: C+H2O→CO+H2. The carbon coated on the catalyst is gradually reformed into CO by steam, and H2 is generated at the same time. In this process, the carbon is peeled off and consumed, so that the catalyst recovers its catalytic activity.

[0037] See also Figure 1 In one embodiment of the present application, a catalyst continuous cycle regeneration methane catalytic cracking hydrogen production device includes a methane catalytic cracking reactor 1, a steam reforming regeneration reactor 2 and a screw conveyor 3; wherein the top of the methane catalytic cracking reactor 1 is provided with a gas production port 111, the upper part is provided with a catalyst feeding port 13, the lower part is provided with a methane distributor 14, and the bottom is connected to the screw conveyor 3; the top of the steam reforming regeneration reactor 2 is connected to the upper part of the methane catalytic cracking reactor 1, the lower part is connected to the screw conveyor 3, and the bottom is provided with a steam distributor 21; the screw conveyor 3 is used to transport the deactivated catalyst falling on the bottom of the methane catalytic cracking reactor 1 to the steam reforming regeneration reactor 2.

[0038] In one application scenario, fresh catalyst is added from the catalyst feeding port 13, with part of the added catalyst falling on the methane distributor 14 and part falling on the bottom; the catalyst feeding port 13 is closed, the methane inlet valve is opened, and the heated methane gas enters the methane catalytic cracking reactor 1 from the methane distributor 14; after passing through the methane distributor 14, a uniform airflow is formed to blow the catalyst into the methane catalytic cracking reactor 1 for fluidization, and at the same time, the catalyst catalyzes methane to generate hydrogen and solid carbon; as the catalytic cracking reaction proceeds, the catalyst is gradually coated by the by-product solid carbon and loses its original shape. During this process, the catalyst particle size and density gradually increase. When the carrier gas is insufficient to support them, they settle to the bottom of the methane catalytic cracking reactor 1 and are transported to the steam reforming regeneration reactor 2 by the screw conveyor 3; water vapor is swept upward by the water vapor distributor 21, and the water vapor contacts the deactivated catalyst to regenerate and re-enter the large-diameter tube 11 of the catalytic cracking reactor 1, completing the continuous cycle of catalysis-deactivation-regeneration-catalysis; the generated hydrogen, residual methane, regenerated gas, and by-product carbon enter the recovery section through the gas production port 111 provided at the top of the methane catalytic cracking reactor 1.

[0039] In this embodiment, optionally, the methane catalytic cracking reactor 1 and the steam reforming regeneration reactor 2 can both be stainless steel cylindrical structures; thermal insulation materials can be attached externally, and an electric heater can be provided between the thermal insulation materials and the reactor as a heating source.

[0040] Optionally, the screw conveyor 3 may be a conventional device, and the conveying direction is from the methane catalytic cracking reactor 1 to the steam reforming regeneration reactor 2 .

[0041] In this embodiment, preferably, the methane catalytic cracking reactor 1 includes a large-diameter tube 11 and a small-diameter tube 12; the top of the large-diameter tube 11 is a gas production port 111, and the side wall is connected to the catalyst feeding port 13 and the top of the steam reforming regeneration reactor 2; the methane distributor 14 is arranged in the small-diameter tube 12, and the bottom is connected to the screw conveyor 3.

[0042] In this embodiment, the setting of the large diameter tube 11 can make the catalyst fluidized there fall back into the reactor due to the reduced flow rate. The by-product carbon particles are small and will not fall back after fluidizing to the large diameter tube 11, thereby achieving the separation of the catalyst and the by-product carbon.

[0043] In this embodiment, optionally, the inner diameter ratio of the large diameter tube 11 to the small diameter tube 12 is 1.2-3.2. Preferably, the inner diameter ratio of the large diameter tube 11 to the small diameter tube 12 can be 1.8.

[0044] In this embodiment, optionally, the inner diameter ratio of the small diameter tube 12 to the steam reforming regeneration reactor 2 is 0.6-1.8. Preferably, the inner diameter ratio of the small diameter tube 12 to the steam reforming regeneration reactor 2 can be 1.

[0045] In this embodiment, preferably, the methane distributor 14 and the water vapor distributor 21 can both be bowl-shaped distributors 4; see Figure 2 and Figure 3 The bowl-shaped distributor 4 includes a bowl body 41 and a bowl cover 42; the bowl body 41 is hollow inside, and an air inlet 411 is provided at the bottom, which can be used for a methane delivery pipe or a water vapor delivery pipe; the bowl cover 42 is provided with a plurality of air outlets 421.

[0046] In this embodiment, a filter element is provided on the bowl cover 42 ; the filter element may be a layer of filter cloth, which can be used to prevent the catalyst from falling into the bowl body 41 .

[0047] In this embodiment, preferably, the bowl body 41 is hemispherical. The spherical curvature of the bowl body 41 can well evenly distribute the gas entering the bowl body 41.

[0048] In this embodiment, optionally, the ratio of the outer diameter of the bowl-shaped distributor 4 to the inner diameter of the small-diameter tube 12 is 0.4-0.8. Preferably, the ratio of the outer diameter of the bowl-shaped distributor 4 to the inner diameter of the small-diameter tube 12 can be 0.7.

[0049] Based on the above embodiments, see Figure 4 One embodiment of the present application provides a hydrogen production system, comprising: a methane storage tank 100, a heater 200, the catalyst continuous cycle regeneration methane catalytic cracking hydrogen production device 300, a condenser 400, a bag-type collector 500, a solid hydrogen storage device 600, and a heat exchanger 700 connected in sequence; wherein the gas output from the methane storage tank 100 enters the heater 200 after heat exchange in the heat exchanger 700, and the gas produced by the catalyst continuous cycle regeneration methane catalytic cracking hydrogen production device 300 enters the condenser 400 after heat exchange in the heat exchanger 700.

[0050] Specifically, the methane gas heated by the heater 200 enters the methane catalytic cracking reactor 1 of the catalyst continuous circulation regeneration methane catalytic cracking hydrogen production device 300 through the methane distributor 14; the gas production port 111 of the methane catalytic cracking reactor 1 is connected to the heat exchanger 700.

[0051] In one application scenario, the outlet gas in the methane storage tank 100 is preheated by the gas produced by the catalyst continuous circulation regeneration methane catalytic cracking hydrogen production device 300 through the heat exchanger 700, and then heated to the catalytic temperature through the heater 200 and enters the catalyst continuous circulation regeneration methane catalytic cracking hydrogen production device 300 for catalytic hydrogen production; the gas produced at the catalytic temperature entering the catalyst continuous circulation regeneration methane catalytic cracking hydrogen production device 300 is cooled by the outlet gas in the methane storage tank 100 through the heat exchanger 700 (waste heat recovery), and then enters the condenser 400 for cooling. The cooled gas enters the bag collector 500 to intercept a small amount of escaping solid carbon, and finally enters the solid hydrogen storage 600 for storage, and the remaining gas is discharged from the top pipe outlet of the solid hydrogen storage 600 and enters the exhaust gas recovery section.

[0052] In summary, the catalyst continuous cycle regeneration methane catalytic cracking hydrogen production device of the present invention is provided with a methane catalytic cracking reactor and a water vapor regeneration reactor in combination, thereby completing the continuous cycle regeneration of the catalyst and improving production efficiency; the deactivated catalyst is regenerated by water vapor, thereby avoiding the safety hazards caused by the entry of oxygen.

[0053] The various devices selected in this application (components whose specific structures are not described) are all universal standard parts or components known to those skilled in the art, and their structures and principles can be known to those skilled in the art through technical manuals or conventional experimental methods.

[0054] In the description of the embodiments of the present invention, unless otherwise clearly specified and limited, the terms "installed", "connected" and "connected" should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral connection.

[0055] In the description of the present invention, it should be noted that the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer," etc., indicating orientations or positional relationships, are based on the orientations or positional relationships shown in the accompanying drawings and are intended solely to facilitate and simplify the description of the present invention. They are not intended to indicate or imply that the devices or components referred to must have, be constructed, or operate in a specific orientation, and therefore should not be construed as limitations on the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0056] With the above-described preferred embodiments of the present invention as a guide, and with reference to the above description, relevant personnel are fully capable of making various changes and modifications without departing from the technical scope of this invention. The technical scope of this invention is not limited to the contents of the specification and must be determined according to the scope of the claims.

Claims

1. A catalyst continuous cycle regeneration methane catalytic cracking hydrogen production device, characterized in that: include: A methane catalytic cracking reactor (1), a steam reforming regeneration reactor (2), and a screw conveyor (3); in The methane catalytic cracking reactor (1) is provided with a gas production port (111) at the top, a catalyst feeding port (13) at the upper portion, a methane distributor (14) at the lower portion, and a screw conveyor (3) at the bottom; The top of the steam reforming regeneration reactor (2) is connected to the upper part of the methane catalytic cracking reactor (1), the lower part is connected to the screw conveyor (3), and the bottom is provided with a steam distributor (21); The screw conveyor (3) is used to convey the deactivated catalyst dropped at the bottom of the methane catalytic cracking reactor (1) into the steam reforming regeneration reactor (2); The methane catalytic cracking reactor (1) comprises a large-diameter tube (11) and a small-diameter tube (12); The top end of the large diameter tube (11) is a gas production port (111), and the side wall is connected to the catalyst feeding port (13) and the top of the steam reforming regeneration reactor (2); The methane distributor (14) is provided in the small-diameter tube (12), and the bottom thereof is connected to the screw conveyor (3); The methane distributor (14) and the water vapor distributor (21) are both bowl-shaped distributors (4); The bowl-shaped distributor (4) comprises a bowl body (41) and a bowl cover (42); the bowl body (41) is hollow inside, and an air inlet (411) is provided at the bottom; and the bowl cover (42) is provided with a plurality of air outlets (421).

2. The catalyst continuous cycle regeneration methane catalytic cracking hydrogen production device according to claim 1 is characterized in that: The inner diameter ratio of the large diameter tube (11) to the small diameter tube (12) is 1.2-3.

2.

3. The catalyst continuous cycle regeneration methane catalytic cracking hydrogen production device according to claim 1 is characterized in that: The inner diameter ratio of the small-diameter tube (12) to the steam reforming regeneration reactor (2) is 0.6-1.

8.

4. The catalyst continuous cycle regeneration methane catalytic cracking hydrogen production device according to claim 1, characterized in that: A filter is provided on the bowl cover (42).

5. The catalyst continuous cycle regeneration methane catalytic cracking hydrogen production device according to claim 1 is characterized in that: The bowl body (41) is hemispherical.

6. The catalyst continuous cycle regeneration methane catalytic cracking hydrogen production device according to claim 1, characterized in that: The ratio of the outer diameter of the bowl-shaped distributor (4) to the inner diameter of the small-diameter tube (12) is 0.4-0.

8.

7. A hydrogen production system, characterized in that: include: A methane storage tank (100), a heater (200), a catalyst continuous cycle regeneration methane catalytic cracking hydrogen production device (300) as described in any one of claims 1 to 6, a condenser (400), a bag-type collector (500), a solid hydrogen storage device (600), and a heat exchanger (700) are connected in sequence; wherein the gas output from the methane storage tank (100) enters the heater (200) after heat exchange in the heat exchanger (700), and the gas produced by the catalyst continuous cycle regeneration methane catalytic cracking hydrogen production device (300) enters the condenser (400) after heat exchange in the heat exchanger (700).

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