Integrated ammonia decomposition hydrogen production and purification membrane reactor with self-heating function

Abstract

An integrated ammonia decomposition hydrogen production and purification membrane reactor with a self-heating function comprises a three-layer sleeve structure, and the reactor is divided into three areas, namely a combustion area, a decomposition area and a permeation area; the area between the casing pipes of the outer layer and the middle layer is a combustion area, and the area is filled with a catalytic combustion catalyst; an area between the middle-layer sleeve and the inner-layer sleeve is a decomposition area, and the area is filled with an ammonia decomposition catalyst; the inner-layer pipe channel is a permeation area; in the combustion area, fuel gas generates heat under the action of a catalytic combustion catalyst, the required temperature is provided for the decomposition area, and combustion waste gas is discharged through an outlet; in the decomposition area, ammonia gas is decomposed into hydrogen and nitrogen under the action of an ammonia decomposition catalyst, the hydrogen permeates into the permeation area through the inner pipe, the nitrogen cannot pass through the inner pipe, and the separation function of the nitrogen and the hydrogen is achieved; the device only needs to be filled with a catalyst and a hydrogen permeable membrane, ammonia decomposition reaction can be carried out without an external heat source, high-purity hydrogen can be obtained, integration of the preparation-separation and purification process is achieved, meanwhile, heat needed by the ammonia decomposition reaction can be supplied to catalytic combustion of hydrogen-containing tail gas in the decomposition area in the combustion area, energy consumption of the reaction is reduced, and energy consumption is reduced. Due to the integrated design, the number of equipment required by the reaction, the occupied area and the volume are reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of ammonia decomposition hydrogen production, and in particular to an integrated ammonia decomposition hydrogen production and purification membrane reactor with a self-heating function. Background Art

[0002] As a clean and efficient secondary energy source, hydrogen energy is widely regarded as one of the most promising energy sources in the 21st century. It has played an increasingly important role in many fields such as transportation, communications, military, and aviation. The large-scale application of hydrogen energy involves multiple links such as hydrogen preparation, separation, purification, storage and transportation. Among them, efficient and safe hydrogen storage technology is the key to promoting the promotion of hydrogen energy, especially providing a cheap hydrogen source for fuel cells and small and medium-sized hydrogen refueling stations. Ammonia, as a hydrogen carrier, has the advantages of high hydrogen storage density (17.6wt%), easy liquefaction, and mature production, storage and transportation technology, making it an ideal choice. Ammonia decomposition to produce hydrogen is a chemical process that refers to heating ammonia to above 600°C and using ruthenium-based or nickel-based catalysts to decompose ammonia into a mixed gas containing 75% hydrogen and 25% nitrogen. The ammonia decomposition hydrogen production process is simple, safe, and low-cost. The product contains no COx impurities, and its theoretical hydrogen storage capacity is significantly higher than other hydrogen production technologies, including water electrolysis (11.1 wt%), methanol-steam reforming (12 wt%), gasoline-steam reforming (12.4 wt%), and hydride hydrolysis (5.2 wt%-8.6 wt%). However, the maximum purity of the hydrogen produced by ammonia decomposition is only 75%, so further separation and purification are required to obtain high-purity hydrogen suitable for use in fuel cells.

[0003] A Chinese invention patent (application number 201911232150.4) discloses an ammonia decomposition membrane reactor, which mainly includes an explosion-proof chamber, a heating and catalytic chamber, a hydrogen separation chamber and other parts. The structural design includes a heater, an electric heating device, an ammonia decomposition catalyst, a palladium membrane and the like. During operation, ammonia is preheated in the heating chamber and then enters the catalyst bed, where it decomposes to produce a hydrogen-rich mixed gas, which is then separated by a palladium membrane to obtain high-purity hydrogen (99.999%). Its special structural design effectively reduces heat loss, reduces energy consumption, and improves heat utilization efficiency. It also removes hydrogen through a palladium membrane to promote the ammonia decomposition reaction and further save energy. However, the reactor uses electric heating to supply heat to the reactor, and the heating of the reactor requires stable power conditions, which not only limits the conditions of use, but also consumes a large amount of electricity.

[0004] A Chinese invention patent (application number 202010919953.3) discloses a self-heating ammonia decomposition reactor, comprising an outer sleeve and an inner sleeve, the inner sleeve is filled with a first catalyst, and the gap between the inner and outer sleeves is filled with a second catalyst. Of the first and second catalysts, one is an ammonia decomposition catalyst and the other is a catalytic combustion catalyst. Under the action of the catalytic combustion catalyst, the fuel gas generates heat and discharges exhaust gas; at the same time, ammonia is decomposed under the action of the ammonia decomposition catalyst, and the required heat comes from the catalytic combustion of the fuel gas. The device does not require an additional burner, simplifies the structure and reduces equipment costs. In the later stage, only the catalytic combustion catalyst needs to be replaced, reducing the difficulty and workload of maintenance. However, the product gas of the reactor is a mixture of hydrogen and nitrogen, which cannot be directly applied to industrial fields such as metallurgy or fuel cells. It needs to be further purified, which increases the difficulty of direct use of hydrogen. Summary of the Invention

[0005] In order to overcome the defects of the above-mentioned prior art, the purpose of the present invention is to propose an integrated ammonia decomposition hydrogen production and purification membrane reactor with self-heating function, which only requires the filling of catalysts and hydrogen permeable membranes, and does not require the additional installation of burners and hydrogen separation devices to carry out ammonia decomposition reactions and obtain high-purity hydrogen, thereby realizing the integration of "production-separation and purification", thereby simplifying the reaction device for ammonia decomposition to produce high-purity hydrogen, solving the defect of high energy consumption of electrically heated ammonia decomposition reactors, and meeting the demand for producing high-purity hydrogen during ammonia decomposition.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] An integrated ammonia decomposition hydrogen production and purification membrane reactor with self-heating function includes an outer casing 10, a middle casing 3 and an inner casing 11 arranged from the outside to the inside. The combustion zone is between the middle casing 3 and the outer casing 10 and is filled with a catalytic combustion catalyst; the decomposition zone is between the inner casing 11 and the middle casing 3 and is filled with an ammonia decomposition catalyst; the inner casing 11 is a permeation zone; one end of the outer casing 10 is provided with a fuel gas inlet 7 and the other end is provided with a combustion waste gas outlet 2; one end of the middle casing 3 is provided with an ammonia inlet 1 and the other end is provided with a decomposition waste gas outlet 8; one end of the inner casing 11 is open and the other end remains sealed.

[0008] The outer wall of the outer sleeve 10 is covered with a heat-insulating material 5 , and the thermocouples 4 penetrate the outer sleeve 10 from both sides.

[0009] A first annular grid plate 6-1 is radially arranged between the outer sleeve 10 and the middle sleeve 3, near one end of the bottom of the outer sleeve 10; the gap of the first annular grid plate 6-1 is 0.5μm-4μm, and the catalytic combustion catalyst is filled above the first annular grid plate 6-1, and the particle size of the catalytic combustion catalyst is not less than the gap of the first annular grid plate 6-1.

[0010] A second annular grid plate 6-2 is radially arranged between the middle casing 3 and the inner casing 11, near one end of the bottom of the middle casing 3; the gap between the second annular grid plate 6-2 is 0.5 μm-4 μm, and an ammonia decomposition catalyst 9 is filled above the second annular grid plate 6-2, and the particle size of the ammonia decomposition catalyst 9 is not less than the gap between the second annular grid plate 6-2.

[0011] The catalytic combustion catalyst is a hydrogen catalytic combustion catalyst, an ammonia catalytic combustion catalyst, or an ammonia-hydrogen combustion mixed catalyst.

[0012] The hydrogen catalytic combustion catalyst includes at least one of MgAl2O4, Mn-Co-Cu-Fe-Ni / γ-Al2O3 / cordierite, Pt / γ-Al2O3 / cordierite, and Pt / CexZr1-xO2 / γ-Al2O3; the ammonia catalytic combustion catalyst includes at least one of Fe2O3, V2O5, Cr2O3, MoOx, and WOx; the ammonia-hydrogen combustion mixed catalyst is a mixture of a hydrogen catalytic combustion catalyst and an ammonia catalytic combustion catalyst, and the ratio of the hydrogen catalytic combustion catalyst to the ammonia catalytic combustion catalyst is not less than 1.

[0013] The ammonia decomposition catalyst is a ruthenium-based ammonia decomposition catalyst or a nickel-based ammonia decomposition catalyst.

[0014] The inner layer casing 11 is a tubular support material and a hydrogen permeable membrane supported on the support material; the maximum permeability of the inner layer casing 11 does not exceed 71%.

[0015] The hydrogen permeable membrane is supported on the tubular support material by chemical plating, electroplating or photocatalytic deposition.

[0016] The tubular support material is made of porous stainless steel or porous ceramics; the hydrogen permeable membrane is made of any one of pure palladium membrane, palladium-silver alloy membrane, palladium-copper alloy membrane, palladium-gold alloy membrane or palladium-ruthenium alloy membrane.

[0017] The technical solution of the present invention has the following advantages:

[0018] 1. The ammonia decomposition membrane reactor with self-heating function provided by the present invention comprises an outer casing and a fuel gas inlet and a combustion waste gas outlet respectively arranged at two ends thereof; a middle casing is arranged between the outer casing and the inner casing, and the middle casing comprises an ammonia inlet and a decomposition waste gas outlet respectively arranged at two ends thereof; the inner casing serves as a permeation zone; an ammonia decomposition catalyst is filled between the inner casing and the middle casing, serving as a decomposition zone, and a catalytic combustion catalyst is filled between the middle casing and the outer casing, serving as a combustion zone; the fuel gas inlet is suitable for communicating with fuel gas, and the fuel gas begins to undergo an exothermic reaction with the catalytic combustion catalyst, thereby simplifying the reaction apparatus for decomposing ammonia to produce high-purity hydrogen and reducing the number of equipment, floor space, and workload required for the reaction.

[0019] 2. In the combustion zone, the fuel gas generates heat under the action of the catalytic combustion catalyst, providing the required temperature for the decomposition zone, and the combustion exhaust gas is discharged through the outlet. In the decomposition zone, the ammonia decomposition catalyst decomposes ammonia into hydrogen and nitrogen. Hydrogen can permeate through the inner tube into the permeation zone, while nitrogen cannot pass through the inner tube, achieving the separation function of nitrogen and hydrogen. This device only requires the filling of the catalyst and hydrogen permeable membrane, without the need for additional burners and hydrogen separation devices to carry out the ammonia decomposition reaction and produce high-purity hydrogen. This realizes the integration of "production, separation and purification", improves the efficiency of high-purity hydrogen production, and solves the high energy consumption problem of electrically heated ammonia decomposition reactors, while meeting the demand for high-purity hydrogen production during ammonia decomposition.

[0020] 3. The self-heating ammonia decomposition membrane reactor provided by the present invention utilizes hydrogen-containing tail gas from the decomposition and purification process as fuel, providing heat for the ammonia decomposition reaction through catalytic combustion. Compared with conventional autothermal and membrane reactors, this reactor not only achieves self-heating but also fully utilizes residual hydrogen from separation and purification, reducing hydrogen waste during the purification process and further improving overall process efficiency.

[0021] In summary, the present invention has the characteristics of simplified structure, low energy consumption and high production efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the specific implementation methods or the description of the prior art. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0023] Figure 1 A cross-sectional view of the structure of the device of the present invention.

[0024] Figure 2 Schematic diagram of the production principle of the device of the present invention.

[0025] Description of reference numerals:

[0026] 1—Ammonia inlet; 2—Combustion waste gas outlet; 3—Middle casing; 4—Thermocouple; 5—Insulation layer; 6-1—First annular grid; 6-2—Second annular grid; 7—Fuel gas inlet; 8—Decomposition waste gas outlet; 9—Ammonia decomposition catalyst; 10—Outer casing; 11—Inner casing; 12—Liquid ammonia storage tank; 13—Expansion valve; 14—Preheater; 15—Gas flowmeter; 16—Gas mixer; 17—Oxygen storage tank. DETAILED DESCRIPTION

[0027] The following will clearly and completely describe the technical solutions of the present invention with reference to the accompanying drawings. Obviously, the embodiments described are only a portion of the embodiments of the present invention, not all of them. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without inventive effort are also within the scope of protection of the present invention.

[0028] In the description of the present invention, it should be noted that the terms "center", "upper", "inner", "outer", etc., indicating directions or positional relationships, are based on the directions or positional relationships shown in the accompanying drawings and are only used to facilitate the description of the present invention and simplify the description. They do not indicate or imply that the device or element referred to must have a specific direction, be constructed and operate in a specific direction. Therefore, they should not be understood as limiting the present invention.

[0029] In the description of the present invention, it should be noted that, unless otherwise expressly specified or limited, the terms "mounted," "connected," and "connected" should be understood broadly. For example, they may refer to fixed, detachable, or integral connections; they may refer to mechanical or electrical connections; they may refer to direct connections or indirect connections through an intermediary; and they may refer to internal communication between two components. Those skilled in the art will understand the specific meanings of these terms in the present invention based on the specific circumstances.

[0030] Example 1

[0031] like Figure 1As shown, this embodiment provides an integrated ammonia decomposition hydrogen production and purification membrane reactor with self-heating function, including an outer casing 10, a middle casing 3 and an inner casing 11 arranged from the outside to the inside, the middle casing 3 and the outer casing 10 are between the combustion zone, which is filled with a catalytic combustion catalyst; the inner casing 11 and the middle casing 3 are between the decomposition zone, which is filled with an ammonia decomposition catalyst; the inner casing 11 is a permeation zone; one end of the outer casing 10 is provided with a fuel gas inlet 7, and the other end is provided with a combustion exhaust gas outlet 2; one end of the middle casing 3 is provided with an ammonia inlet 1, and the other end is provided with a decomposition exhaust gas outlet 8; one end of the inner casing 11 is open, and the other end remains sealed.

[0032] The fuel gas inlet 7 is suitable for connecting fuel gas, which is suitable for exothermic reaction with the catalytic combustion catalyst. The fuel gas enters the combustion zone between the outer casing 10 and the middle casing 3 through the fuel gas inlet 7. When flowing through the catalytic combustion catalyst, an exothermic reaction occurs, and the combustion exhaust gas is discharged through the combustion exhaust gas outlet 2. Ammonia enters the decomposition zone between the middle casing 3 and the inner casing 11 through the ammonia inlet 1. Under the action of the ammonia decomposition catalyst 9, it decomposes to produce hydrogen and nitrogen. The heat required for the process comes from the combustion zone. A portion of the hydrogen produced in the decomposition zone penetrates into the tube through the inner casing 11, and the remaining hydrogen and nitrogen are discharged through the decomposition exhaust gas outlet 8. The gas discharged from the decomposition exhaust gas outlet 8 is collected, processed, and mixed with oxygen, and can be used as fuel gas to provide heat for the reactor. Therefore, this device can achieve independent operation and "production-separation and purification" integration of ammonia decomposition and hydrogen production without the need for additional heat generation equipment and hydrogen separation and purification equipment, thereby simplifying the equipment and operating process and reducing equipment costs.

[0033] A first annular grid plate 6-1 is radially arranged between the outer sleeve 10 and the middle sleeve 3, near one end of the bottom of the outer sleeve 10; the gap of the first annular grid plate 6-1 is 0.5μm-4μm, and the catalytic combustion catalyst is filled above the first annular grid plate 6-1, and the particle size of the catalytic combustion catalyst is not less than the gap of the first annular grid plate 6-1.

[0034] A second annular grid plate 6-2 is radially arranged between the middle casing 3 and the inner casing 11, near one end of the bottom of the middle casing 3; the gap between the second annular grid plate 6-2 is 0.5 μm-4 μm, and an ammonia decomposition catalyst 9 is filled above the second annular grid plate 6-2, and the particle size of the ammonia decomposition catalyst 9 is not less than the gap between the second annular grid plate 6-2.

[0035] The catalytic combustion catalyst is a hydrogen catalytic combustion catalyst, an ammonia catalytic combustion catalyst, or an ammonia-hydrogen combustion mixed catalyst.

[0036] The hydrogen catalytic combustion catalyst includes at least one of MgAl2O4, Mn-Co-Cu-Fe-Ni / γ-Al2O3 / cordierite, Pt / γ-Al2O3 / cordierite, and Pt / CexZr1-xO2 / γ-Al2O3; the ammonia catalytic combustion catalyst includes at least one of Fe2O3, V2O5, Cr2O3, MoOx, and WOx; the ammonia-hydrogen combustion mixed catalyst is a mixture of a hydrogen catalytic combustion catalyst and an ammonia catalytic combustion catalyst, and the ratio of the hydrogen catalytic combustion catalyst to the ammonia catalytic combustion catalyst is not less than 1.

[0037] The ammonia decomposition catalyst is a ruthenium-based ammonia decomposition catalyst or a nickel-based ammonia decomposition catalyst.

[0038] The inner sleeve 11 is a tubular support material and a hydrogen permeable membrane supported on the support material.

[0039] The hydrogen permeable membrane is supported on the tubular support material by chemical plating, electroplating or photocatalytic deposition.

[0040] The tubular support material is made of porous stainless steel or porous ceramics; the hydrogen permeable membrane is made of any one of pure palladium membrane, palladium-silver alloy membrane, palladium-copper alloy membrane, palladium-gold alloy membrane or palladium-ruthenium alloy membrane.

[0041] The ammonia decomposition membrane reactor with self-heating function must ensure that the reactor can fully realize self-heating operation and take into account the 10% heat loss in the combustion zone. The maximum permeability of the inner casing 11 shall not exceed 71%.

[0042] As an optional embodiment, the fuel gas inlet and the decomposition waste gas outlet are located on the same side, and the ammonia inlet and the combustion waste gas outlet are located on the same side; or, the fuel gas inlet and the ammonia inlet are located on the same side, and the combustion waste gas outlet and the decomposition waste gas outlet are located on the same side.

[0043] The inner sleeve is kept open on one side and sealed on the other side, and the open side is on the same side as the ammonia inlet; or, the inner sleeve is kept open on one side and sealed on the other side, and the open side is on opposite sides of the ammonia inlet.

[0044] Specifically, the ammonia decomposition membrane reactor with self-heating function includes: a first annular grid plate 6-1, which is close to the combustion exhaust gas outlet 7, arranged in the combustion zone, connected to the inner wall of the outer casing 10 and the outer wall of the middle casing 3, and the upper area is filled with catalytic combustion catalyst; a decomposition zone between the middle casing 3) and the inner casing 11, in which a second annular grid plate is arranged close to the decomposition exhaust gas outlet side, and is connected to the inner wall of the middle casing 3 and the outer wall of the inner casing 11, and the upper area is filled with an ammonia decomposition catalyst 9.

[0045] The heat-insulating material 5 is arranged on the outer wall of the outer casing 10 to reduce the amount of heat released to the environment during combustion of the combustion gas and improve the energy utilization efficiency of the system.

[0046] Thermocouples 4 penetrate the outer sleeve 10 from both sides and are used to monitor the temperature of the reactor during the reaction process.

[0047] See also Figure 2 , the working principle of the present invention is:

[0048] First, the liquid ammonia in the liquid ammonia storage tank 12 passes through the expansion valve 13 to convert it into ammonia gas. The ammonia gas then passes through the preheater 14, where it heats up after exchanging heat with high-purity hydrogen. It then flows through the gas flowmeter 15 and the ammonia inlet 1 into the decomposition zone in the middle casing 3, where an ammonia decomposition reaction occurs, producing nitrogen and hydrogen. As the reaction proceeds, some of the hydrogen produced by the ammonia decomposition permeates into the inner casing 11, with the permeation ratio determined by the pressure difference between the middle casing 3 and the inner casing 11 and the type of hydrogen permeable membrane. After the permeation purification, the high-purity hydrogen flows out, exchanges heat with ammonia in the preheater 14, and then cools down to produce the final hydrogen product. In the middle casing 3, the remaining unpermeated hydrogen is discharged through the decomposition waste gas outlet 8 and mixed with oxygen from the oxygen storage tank 17 in a gas mixer 16 at a 1:1 ratio. The resulting mixed gas becomes the fuel gas. The fuel gas flows out of the gas mixer 16, passes through the gas flow meter 15 and the fuel gas inlet 7, and enters the combustion zone in the outer casing 10, where a hydrogen catalytic combustion reaction occurs to produce water. The combustion exhaust gas is discharged through the combustion exhaust gas outlet 2.

[0049] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will appreciate that other variations or modifications can be made based on the above description. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. An integrated ammonia decomposition hydrogen production and purification membrane reactor with self-heating function, comprising an outer casing (10), a middle casing (3) and an inner casing (11) arranged from the outside to the inside, characterized in that: The combustion zone is between the middle sleeve (3) and the outer sleeve (10), which is filled with a catalytic combustion catalyst; the decomposition zone is between the inner sleeve (11) and the middle sleeve (3), which is filled with an ammonia decomposition catalyst; the inner sleeve (11) is a permeation zone; one end of the outer sleeve (10) is provided with a fuel gas inlet (7), and the other end is provided with a combustion waste gas outlet (2); one end of the middle sleeve (3) is provided with an ammonia inlet (1), and the other end is provided with a decomposition waste gas outlet (8); one end of the inner sleeve (11) is open, and the other end remains sealed.

2. The integrated ammonia decomposition hydrogen production and purification membrane reactor with self-heating function according to claim 1, characterized in that: The outer wall of the outer sleeve (10) is covered with a heat-insulating material (5), and the thermocouples (4) penetrate the outer sleeve (10) from both sides.

3. The integrated ammonia decomposition hydrogen production and purification membrane reactor with self-heating function according to claim 1, characterized in that: A first annular grid plate (6-1) is radially arranged between the outer sleeve (10) and the middle sleeve (3), at one end close to the bottom of the outer sleeve (10); the gap of the first annular grid plate (6-1) is 0.5 μm-4 μm, and a catalytic combustion catalyst is filled above the first annular grid plate (6-1), and the particle size of the catalytic combustion catalyst is not less than the gap of the first annular grid plate (6-1).

4. The integrated ammonia decomposition hydrogen production and purification membrane reactor with self-heating function according to claim 1, characterized in that: A second annular grid plate (6-2) is radially arranged between the middle casing (3) and the inner casing (11), near one end of the bottom of the middle casing (3); the gap between the second annular grid plate (6-2) is 0.5 μm-4 μm, and an ammonia decomposition catalyst (9) is filled above the second annular grid plate (6-2); the particle size of the ammonia decomposition catalyst (9) is not less than the gap between the second annular grid plate (6-2).

5. The integrated ammonia decomposition hydrogen production and purification membrane reactor with self-heating function according to claim 1 or 3, characterized in that: The catalytic combustion catalyst is a hydrogen catalytic combustion catalyst, an ammonia catalytic combustion catalyst, or an ammonia-hydrogen combustion mixed catalyst.

6. The integrated ammonia decomposition hydrogen production and purification membrane reactor with self-heating function according to claim 5, characterized in that: The hydrogen catalytic combustion catalyst includes at least one of MgAl2O4, Mn-Co-Cu-Fe-Ni / γ-Al2O3 / cordierite, Pt / γ-Al2O3 / cordierite, and Pt / CexZr1-xO2 / γ-Al2O3; the ammonia catalytic combustion catalyst includes at least one of Fe2O3, V2O5, Cr2O3, MoOx, and WOx; the ammonia-hydrogen combustion mixed catalyst is a mixture of a hydrogen catalytic combustion catalyst and an ammonia catalytic combustion catalyst, and the ratio of the hydrogen catalytic combustion catalyst to the ammonia catalytic combustion catalyst is not less than 1.

7. The integrated ammonia decomposition hydrogen production and purification membrane reactor with self-heating function according to claim 1 or 4, characterized in that: The ammonia decomposition catalyst is a ruthenium-based ammonia decomposition catalyst or a nickel-based ammonia decomposition catalyst.

8. The integrated ammonia decomposition hydrogen production and purification membrane reactor with self-heating function according to claim 1, characterized in that: The inner layer casing (11) is a tubular support material and a hydrogen permeable membrane loaded on the support material; the maximum permeability of the inner layer casing (11) does not exceed 71%.

9. The integrated ammonia decomposition hydrogen production and purification membrane reactor with self-heating function according to claim 8, characterized in that: The hydrogen permeable membrane is supported on the tubular support material by chemical plating, electroplating or photocatalytic deposition.

10. The integrated ammonia decomposition hydrogen production and purification membrane reactor with self-heating function according to claim 8, characterized in that: The tubular support material is made of porous stainless steel or porous ceramics; the hydrogen permeable membrane is made of any one of pure palladium membrane, palladium-silver alloy membrane, palladium-copper alloy membrane, palladium-gold alloy membrane or palladium-ruthenium alloy membrane.

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