Ammonia decomposition hydrogen permeation reactor utilizing magnetron sputtering coating technology

Abstract

The invention discloses an ammonia decomposition hydrogen permeation reactor utilizing magnetron sputtering coating technology, which comprises a first flange and a second flange, the first flange is embedded in the second flange and is fastened by standard M6 bolts uniformly distributed on the circumference and matched nuts and gaskets thereof, a cavity is formed between the two flanges, and the cavity is communicated with the cavity. A three-way pipe is welded to the through hole formed in the first flange, one port of the three-way pipe is an ammonia gas inlet, the other port of the three-way pipe is a nitrogen outlet, a pipe is welded to the through hole formed in the second flange, the port of the pipe is a hydrogen outlet, and the three-way pipe is communicated with the cavity and the pipe welded to the through hole of the second flange. A first carbon gasket and a second carbon gasket are placed in the cavity, and a reaction film is arranged between the second carbon gasket and the first carbon gasket. According to the reactor, the magnetron sputtering coating technology and a high-hydrogen-permeability selective material are combined, the hydrogen extraction efficiency is greatly improved, and the economical efficiency and practicability of the whole ammonia decomposition hydrogen production process are enhanced.

Description

Technical Field

[0001] The invention belongs to the field of new energy hydrogen production, and specifically relates to an ammonia decomposition hydrogen permeation reactor utilizing magnetron sputtering coating technology. Background Art

[0002] On August 11, 2024, the "Opinions on Accelerating the Comprehensive Green Transformation of Economic and Social Development" was issued, proposing to promote the development of the entire chain of hydrogen energy "production, storage, transmission and use", establish and improve hydrogen energy "production, storage, transmission and use" standards, etc., providing clear directions and requirements for the development of the hydrogen energy industry. With the growing global demand for clean energy and the increasingly urgent demand for efficient and sustainable hydrogen supply in the industrial field, ammonia decomposition hydrogen production technology has attracted widespread attention as a highly promising hydrogen production method. Ammonia (NH3) has the advantages of high hydrogen content (17.65% mass fraction), easy storage and transportation, etc., through the ammonia decomposition reaction It is possible to efficiently produce hydrogen under appropriate conditions, and the reaction process is relatively clean. The hydrogen produced has key applications in many fields such as fuel cells and chemical synthesis.

[0003] Conventional ammonia decomposition reactors mostly use granular catalysts filled in the reaction tube to promote the reaction. However, the active components of granular catalysts are unevenly dispersed and prone to agglomeration, resulting in insufficient utilization of active sites, which in turn affects the overall rate of the ammonia decomposition reaction and the efficiency of hydrogen production. Moreover, as the use time increases, granular catalysts are prone to sintering and deactivation, which greatly shortens the effective service life of the reactor and increases operating costs and maintenance frequency.

[0004] As an advanced thin film preparation method, magnetron sputtering coating technology has shown unique advantages in material surface modification and functionalization. It can precisely control the thickness, composition and microstructure of the film layer at a low substrate temperature to achieve atomic-level material deposition. Through this technology, metals or alloy elements with high catalytic activity and membrane materials with high selective permeability to hydrogen can be accurately deposited on a suitable substrate to form a thin film coating with excellent catalytic and hydrogen permeability functions.

[0005] This technology is applied to the preparation of ammonia decomposition hydrogen permeation reactors, which is expected to solve the problems of existing reactors in catalytic performance, material properties, reaction efficiency and other aspects, and create a new type of ammonia decomposition hydrogen permeation reactor that is efficient, stable and can achieve high-quality hydrogen output and separation and extraction, to meet the current and future growing demand for hydrogen in the fields of clean energy and industrial hydrogen, and to promote ammonia decomposition hydrogen production technology to a new stage of development. Summary of the invention

[0006] In view of the problems existing in the prior art, the purpose of the present invention is to provide an ammonia decomposition hydrogen permeation reactor using magnetron sputtering coating technology to overcome the shortcomings of sintering and deactivation of particle catalysts in the existing ammonia decomposition hydrogen production process that affects the service life of the reactor.

[0007] To achieve the above object, the technical solution of the present invention is as follows: A reactor for ammonia decomposition and hydrogen permeation using magnetron sputtering coating technology comprises a first flange and a second flange, wherein the first flange is embedded in the second flange and fastened by standard M6 bolts uniformly distributed around the circumference and their matching nuts and washers, a chamber is formed between the two flanges, a three-way pipe is welded to a through hole opened on the first flange, wherein one end of the three-way pipe is an ammonia inlet and the other end is a nitrogen outlet, a pipe is welded to a through hole opened on the second flange, and a port of the pipe is a hydrogen outlet, wherein the three-way pipe is connected to the chamber and the pipe welded to the through hole of the second flange, a first carbonaceous gasket and a second carbonaceous gasket are placed inside the chamber, and a reaction membrane is provided between the second carbonaceous gasket and the first carbonaceous gasket.

[0008] Furthermore, the reaction membrane comprises a metal membrane, the metal membrane is plated with a membrane layer, one end of the reaction membrane is adjacent to an ammonia inlet, and the other end is adjacent to a hydrogen outlet.

[0009] Furthermore, the first flange is recessed inwardly toward the end of the second flange, and is nested with the second flange to form a small chamber, wherein the space inside the chamber is just enough to accommodate the first and second carbonaceous gaskets and the metal diaphragm fixed between the two carbonaceous gaskets.

[0010] Furthermore, the first and second carbonaceous gaskets are both made of high temperature resistant and non-deformable materials, and the two carbonaceous gaskets are interference fit with the first flange.

[0011] Furthermore, a high temperature resistant rubber gasket is provided between the nested combination of the first flange and the second flange, and the high temperature resistant rubber gasket and the second flange are in interference fit.

[0012] Furthermore, the metal diaphragm is metal niobium or metal tantalum, and the film layer is a self-prepared cobalt-molybdenum nitride catalyst, and the catalyst is plated on the metal diaphragm by magnetron sputtering technology.

[0013] Furthermore, it includes an ammonia bottle, a gas washing bottle, a drying bottle, a nitrogen storage tank and a hydrogen storage tank, the ammonia bottle is connected to the ammonia inlet through a pipeline, the nitrogen outlet is connected to the gas inlet of the gas washing bottle through a pipeline, the gas outlet of the gas washing bottle is connected to the gas inlet of the drying bottle through a pipeline, the gas outlet of the drying bottle is connected to the gas inlet of the nitrogen storage tank through a pipeline, and the hydrogen outlet is connected to the gas inlet of the hydrogen storage tank through a pipeline.

[0014] Furthermore, it includes a gas chromatograph, the gas outlet of the nitrogen storage tank is connected to the gas chromatograph through a pipeline, and the gas outlet of the hydrogen storage tank is connected to the gas chromatograph through a pipeline.

[0015] Furthermore, a valve 1 is provided on the pipeline connecting the ammonia bottle and the ammonia inlet; a valve 2 is provided on the pipeline connecting the nitrogen outlet and the gas inlet of the gas washing bottle.

[0016] Furthermore, it comprises a heating furnace, and the reactor is placed in the heating furnace.

[0017] Compared with the prior art, the beneficial effects of the present invention are as follows: 1) The present invention uses metal niobium or metal tantalum as a hydrogen permeable membrane, and deposits highly active catalytic components, cobalt molybdenum nitride, on the surface of the metal membrane with atomic-level uniformity through magnetron sputtering technology. The reaction is heated by a heating furnace to provide reaction conditions. During the reaction, ammonia in the ammonia bottle enters the ammonia inlet through valve control, and is heated by a heating furnace to reach the reaction temperature. The ammonia contacts the membrane catalyst for decomposition, and the generated hydrogen enters the hydrogen storage tank from the hydrogen outlet position using the hydrogen permeability selectivity of the metal membrane. The product purity is tested by a gas chromatograph to verify that the product has a high purity. The byproduct nitrogen generated in the reaction also reaches a high purity through a washing and drying process, and can be collected for other purposes; 2) The reactor of the present invention combines magnetron sputtering coating technology with highly hydrogen permeable selective materials, which greatly improves the hydrogen extraction efficiency and enhances the economy and practicality of the entire ammonia decomposition hydrogen production process; 3) The present invention utilizes magnetron sputtering coating technology to deposit highly active catalytic components at key locations of the reactor with atomic-level uniformity, forming a highly dispersed and stable catalytic film. Compared with traditional granular catalysts, this thin film catalyst greatly increases the number of exposed active sites, effectively avoiding the agglomeration of active components, allowing ammonia molecules to more fully contact the active sites and undergo decomposition reactions; during long-term operation, the thin film catalyst is not prone to sintering and deactivation problems, and has good structural stability, thereby significantly extending the service life of the reactor, reducing the operating cost and maintenance workload caused by frequent catalyst replacement, and ensuring the continuous and efficient process of ammonia decomposition and hydrogen production; 4) The present invention can accurately prepare a thin film material with high selective permeability to hydrogen through magnetron sputtering coating technology. The thin film can efficiently allow hydrogen to permeate based on the differences in size and adsorption characteristics between hydrogen molecules and other gas molecules (such as nitrogen generated by the reaction), while also acting as a barrier to other gases; the hydrogen generated in this way can be quickly separated from the reactor with high purity and collected for utilization, which greatly improves the extraction efficiency of hydrogen, reduces the burden of subsequent purification processes, and further enhances the economic and practical advantages of the entire ammonia decomposition hydrogen production process; 5) Based on the characteristics of magnetron sputtering coating technology, the present invention can easily adapt to the specific requirements of ammonia decomposition and hydrogen production in different scales and different application scenarios by adjusting the coating composition, thickness, deposition position and other parameters; whether it is a small laboratory-level hydrogen production demand or a large-scale industrial production of hydrogen application scenario, the reactor can be optimized through targeted coating design, so that it has good versatility and scalability, laying a solid foundation for the promotion and application of ammonia decomposition and hydrogen production technology in more fields; 6) The metal diaphragm used in the present invention is metal niobium or metal tantalum. Tantalum has extremely high chemical corrosion resistance, second only to precious metals, and is not easily corroded in a variety of harsh chemical environments. This allows the hydrogen permeable material containing niobium and tantalum to work stably in a complex chemical environment and extend its service life. The melting point of tantalum is as high as 3000°C, second only to tungsten and rhenium. The melting point of niobium is also relatively high. Both can withstand high temperature environments and are suitable for hydrogen permeation reactions carried out under high temperature conditions, ensuring the efficiency and stability of the hydrogen permeation process. Tantalum is good at capturing hydrogen and can spit out captured hydrogen particles at high temperatures. The material can be regenerated for reuse. This feature is conducive to improving the use efficiency and economy of hydrogen permeable materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 A schematic diagram of the structure of an ammonia decomposition hydrogen permeation reactor using magnetron sputtering coating technology provided by an embodiment of the present invention; Figure 2 A structural side view of an ammonia decomposition hydrogen permeation reactor using magnetron sputtering coating technology provided by an embodiment of the present invention; Figure 3 A diagram of an experimental system of an ammonia decomposition hydrogen permeation reactor using magnetron sputtering coating technology provided in an embodiment of the present invention.

[0019] In the figure: 1. ammonia inlet; 2. nitrogen outlet; 3. nut; 4. gasket; 5. M6 bolt; 6. second flange; 7. hydrogen outlet; 8. high temperature resistant rubber gasket; 9. carbonaceous gasket one; 10. metal diaphragm; 11. membrane layer; 12. carbonaceous gasket two; 13. first flange; 201. ammonia bottle; 202. valve one; 203. heating furnace; 204. hydrogen storage tank; 205. gas chromatograph; 206. nitrogen storage tank; 207. drying bottle; 208. gas washing bottle; 209. valve two. DETAILED DESCRIPTION

[0020] The present invention will be further described below in conjunction with the accompanying drawings, but the scope of protection of the present invention is not limited to the described scope.

[0021] Please refer to Figure 1-3A reactor for ammonia decomposition and hydrogen permeation using magnetron sputtering coating technology, comprising a first flange 13 and a second flange 6, wherein the first flange 13 is embedded in the second flange 6 and is fastened by 6 standard M6 bolts 5 and matching nuts 3 and gaskets 4 evenly distributed around the circumference, and a chamber is formed between the two flanges, a through hole opened on the first flange 13 is welded with a tee pipe, wherein one end of the tee pipe is an ammonia inlet 1 and the other end is a nitrogen outlet 2, a through hole opened on the second flange 6 is welded with a pipe, and the end of the pipe is a hydrogen outlet 7, wherein the tee pipe is connected with the chamber and the pipe welded to the through hole of the second flange 6, a carbonaceous gasket 1 9 and a carbonaceous gasket 2 12 are placed inside the chamber, and a reaction membrane is arranged between the carbonaceous gasket 2 12 and the carbonaceous gasket 1 9.

[0022] The reaction membrane includes a metal diaphragm 10, and the metal diaphragm 10 is coated with a film layer 11. One end of the reaction membrane is adjacent to the ammonia inlet 1, and the other end is adjacent to the hydrogen outlet 7. The present invention uses metal niobium or metal tantalum as a hydrogen permeable membrane, and deposits the highly active catalytic component cobalt molybdenum nitride on the surface of the metal diaphragm with atomic-level uniformity through magnetron sputtering technology. Further, the metal diaphragm 10 is metal niobium or metal tantalum, which is mainly used for its certain permeability to hydrogen. Under appropriate temperature and pressure conditions, hydrogen atoms can diffuse in the niobium or tantalum lattice. The film layer 11 is a self-prepared cobalt molybdenum nitride catalyst, which has a higher ammonia decomposition efficiency under relatively low temperature conditions. The catalyst is plated on the metal diaphragm 10 through magnetron sputtering technology, forming the core component of the reactor.

[0023] The metal diaphragm 10 used in the present invention is metal niobium or metal tantalum. Tantalum has extremely high chemical corrosion resistance, second only to precious metals, and is not easily corroded in a variety of harsh chemical environments. This allows the hydrogen permeable material containing niobium and tantalum to work stably in a complex chemical environment and extend its service life. The melting point of tantalum is as high as 3000°C, second only to tungsten and rhenium. The melting point of niobium is also relatively high. Both can withstand high temperature environments and are suitable for hydrogen permeation reactions carried out under high temperature conditions, ensuring the efficiency and stability of the hydrogen permeation process. Tantalum is good at capturing hydrogen and can spit out captured hydrogen particles at high temperatures. The material can be regenerated for reuse. This feature is conducive to improving the use efficiency and economy of hydrogen permeable materials.

[0024] The first flange 13 is recessed inwardly toward the end of the second flange 6, and is nested with the second flange 6 to form a small chamber, wherein the space inside the chamber is just enough to accommodate the carbonaceous gasket 1 9, the carbonaceous gasket 2 12, and the metal diaphragm 10 fixed between the two carbonaceous gaskets.

[0025] Both the carbonaceous gasket 1 9 and the carbonaceous gasket 2 12 are made of high temperature resistant and non-deformable materials, and the two carbonaceous gaskets are interference fit with the first flange 13, which ensures the airtightness in the chamber to a certain extent and prevents the gas from escaping from the gap without reaction. The carbonaceous gasket 1 9 and the carbonaceous gasket 2 12 tightly fix the metal diaphragm 10 in the middle, with the purpose of fixing the metal diaphragm 10 so that it remains in a vertical position during the reaction to ensure the full progress of the reaction.

[0026] A high temperature resistant rubber gasket 8 is provided between the nested combination of the first flange 13 and the second flange 6. The high temperature resistant rubber gasket 8 and the second flange 6 are interference fit. In addition to not deforming and melting in the high temperature reaction, the high temperature resistant rubber gasket 8 mainly plays the role of ensuring the air tightness of the chamber to ensure that the gas does not escape through the fitting gap between the first flange 13 and the second flange 6.

[0027] The present invention discloses an ammonia decomposition hydrogen permeation reactor experimental system using magnetron sputtering coating technology, comprising an ammonia bottle 201, a gas washing bottle 208, a drying bottle 207, a nitrogen storage tank 206 and a hydrogen storage tank 204, wherein the ammonia bottle 201 is connected to an ammonia inlet 1 through a pipeline, a nitrogen outlet 2 is connected to a gas inlet of the gas washing bottle 208 through a pipeline, a gas outlet of the gas washing bottle 208 is connected to a gas inlet of the drying bottle 207 through a pipeline, a gas outlet of the drying bottle 207 is connected to a gas inlet of the nitrogen storage tank 206 through a pipeline, and a hydrogen outlet 7 is connected to a gas inlet of the hydrogen storage tank 204 through a pipeline, and is responsible for collecting main products.

[0028] The experimental system of the present invention includes a gas chromatograph 205, a gas outlet of a nitrogen storage tank 206 is connected to the gas chromatograph 205 through a pipeline, and a gas outlet of a hydrogen storage tank 204 is connected to the gas chromatograph 205 through a pipeline. Both the hydrogen storage tank 204 and the nitrogen storage tank 206 can be connected to the gas chromatograph 205 through an additional pipeline to conduct gas composition research and determine the purity of the product.

[0029] Furthermore, a valve 202 is provided on the pipeline connecting the ammonia bottle 201 and the ammonia inlet 1; a valve 209 is provided on the pipeline connecting the nitrogen outlet 2 and the gas inlet of the washing bottle 208. At the beginning of the reaction, valve 202 is opened and valve 209 is closed. During the reaction, since the metal diaphragm 10 is only responsible for the permeation of hydrogen, the product nitrogen will remain in the air inlet pipe and the reaction chamber. After reaching a certain amount, the accumulated nitrogen can be released by closing valve 202 and opening valve 209. After a period of time, the operation at the beginning of the reaction is repeated to continue the reaction.

[0030] When the nitrogen outlet 2 opens valve 209 to release gas, a certain amount of ammonia will be contained in the nitrogen. Therefore, the ammonia is absorbed by the acid solution built into the washing bottle 208, and water vapor is absorbed by the drying bottle 207 to obtain pure nitrogen that is passed into the nitrogen storage tank 206.

[0031] The experimental system of the present invention further comprises a heating furnace 203 , and the reactor is placed in the heating furnace 203 .

[0032] The specific operation steps of an ammonia decomposition hydrogen permeation reactor using magnetron sputtering coating technology in ammonia decomposition hydrogen production are as follows: a. Open the ammonia bottle 201, valve 1 202 and valve 2 209, disconnect the washing bottle 208, turn on the heating furnace 203, set the working temperature, and after reaching the working temperature, close the valve 209, connect the washing bottle 208, and pass a certain ammonia flow rate into the ammonia inlet 1 and the cavity; b. Wait for the reaction to proceed, observe the hydrogen filling situation inside the hydrogen storage tank 204, connect the hydrogen storage tank 204 and the gas chromatograph 205, open the outlet of the hydrogen storage tank 204, and open the gas chromatograph 205 to detect the purity of the hydrogen product produced by the reaction. After the detection is completed, close the gas chromatograph 205 and disconnect it from the hydrogen storage tank 204; c. After the reaction reaches a certain time, close valve 1 202, keep valve 2 209 open, guide the mixed gas of ammonia and nitrogen into the washing bottle 208 and the drying bottle 207, observe the nitrogen storage situation of the nitrogen storage tank 206, connect the nitrogen storage tank 206 and the gas chromatograph 205, turn on the gas chromatograph 205, detect the purity of the product nitrogen, and close the gas chromatograph 205 after the detection; d. After there is no obvious change in the nitrogen storage tank 206, close the second valve 209, open the first valve 202, and repeat step a; e. After the reaction is completed, turn off the heating furnace 203, wait for the heating furnace to cool to room temperature, turn off the ammonia bottle 201, open valve 209, disconnect the washing bottle 208, discharge the gas at the inlet and in the cavity, and after the pressure displayed on the ammonia bottle 201 returns to zero, close valve 1 202, and after a period of time, close valve 209 to end the operation.

[0033] In this embodiment, the metal diaphragm uses a niobium sheet or a tantalum sheet as a hydrogen permeable substrate, with a diameter of 30 mm and a thickness of 0.01 mm. The outlet pressure of the ammonia bottle is set to 0.1 MPa, and the heating furnace is set to rise to 600°C for 120 minutes. When cooling, the heating furnace is directly turned off and waited to naturally drop to room temperature. The metal diaphragm is plated with a homemade cobalt-molybdenum nitride catalyst on the surface through magnetron sputtering technology. The catalyst has an ammonia decomposition efficiency of about 90% at a set temperature of 600°C, which can basically achieve complete decomposition of ammonia. The outlet tail gas is analyzed by gas chromatograph, and no ammonia components are detected, indicating that the ammonia is completely converted and the hydrogen purity is high.

Claims

1. An ammonia decomposition hydrogen permeation reactor using magnetron sputtering coating technology, characterized in that The invention comprises a first flange (13) and a second flange (6), wherein the first flange (13) is embedded in the second flange (6) and is fastened by standard M6 bolts (5) and matching nuts (3) and gaskets (4) uniformly distributed around the circumference, and a chamber is formed between the two flanges. A tee is welded to a through hole opened on the first flange (13), wherein one end of the tee is an ammonia inlet (1) and the other end is a nitrogen outlet (2), and a pipe is welded to a through hole opened on the second flange (6), wherein a port of the pipe is a hydrogen outlet (7), wherein the tee is connected to the chamber and the pipe welded to the through hole of the second flange (6), and a first carbonaceous gasket (9) and a second carbonaceous gasket (12) are placed inside the chamber, and a reaction membrane is provided between the second carbonaceous gasket (12) and the first carbonaceous gasket (9).

2. The ammonia decomposition dialysis reactor using magnetron sputtering coating technology according to claim 1, characterized in that The reaction membrane comprises a metal membrane (10), the metal membrane (10) being plated with a membrane layer (11), one end of the reaction membrane being adjacent to an ammonia inlet (1), and the other end being adjacent to a hydrogen outlet (7).

3. The ammonia decomposition dialysis reactor using magnetron sputtering coating technology according to claim 2, characterized in that The first flange (13) is recessed inwardly toward the end of the second flange (6), and is nested with the second flange (6) to form a small chamber, wherein the space inside the chamber is just enough to accommodate the first carbonaceous gasket (9) and the second carbonaceous gasket (12) as well as the metal diaphragm (10) fixed between the two carbonaceous gaskets.

4. The ammonia decomposition dialysis reactor using magnetron sputtering coating technology according to claim 3, characterized in that The first carbonaceous gasket (9) and the second carbonaceous gasket (12) are both made of high temperature resistant and non-deformable materials, and the two carbonaceous gaskets are interference fit with the first flange (13).

5. The ammonia decomposition dialysis reactor using magnetron sputtering coating technology according to claim 1, characterized in that A high temperature resistant rubber gasket (8) is provided between the nested combination of the first flange (13) and the second flange (6), and the high temperature resistant rubber gasket (8) and the second flange (6) are in an interference fit.

6. The ammonia decomposition dialysis reactor using magnetron sputtering coating technology according to claim 2, characterized in that The metal diaphragm (10) is metal niobium or metal tantalum, and the film layer (11) is a self-prepared cobalt-molybdenum nitride catalyst, which is plated on the metal diaphragm (10) by magnetron sputtering technology.

7. The ammonia decomposition hydrogen permeation reactor using magnetron sputtering coating technology according to claim 1, characterized in that The invention comprises an ammonia bottle (201), a gas washing bottle (208), a drying bottle (207), a nitrogen storage tank (206) and a hydrogen storage tank (204), wherein the ammonia bottle (201) is connected to an ammonia inlet (1) via a pipeline, the nitrogen outlet (2) is connected to a gas inlet of the gas washing bottle (208) via a pipeline, the gas outlet of the gas washing bottle (208) is connected to a gas inlet of the drying bottle (207) via a pipeline, the gas outlet of the drying bottle (207) is connected to a gas inlet of the nitrogen storage tank (206) via a pipeline, and the hydrogen outlet (7) is connected to a gas inlet of the hydrogen storage tank (204) via a pipeline.

8. The ammonia decomposition and hydrogen permeation reactor using magnetron sputtering coating technology according to claim 7, characterized in that It comprises a gas chromatograph (205), wherein a gas outlet of the nitrogen storage tank (206) is connected to the gas chromatograph (205) via a pipeline, and a gas outlet of the hydrogen storage tank (204) is connected to the gas chromatograph (205) via a pipeline.

9. The ammonia decomposition and hydrogen permeation reactor using magnetron sputtering coating technology according to claim 7, characterized in that A valve 1 (202) is provided on the pipeline connecting the ammonia bottle (201) and the ammonia inlet (1); a valve 2 (209) is provided on the pipeline connecting the nitrogen outlet (2) and the gas inlet of the gas washing bottle (208).

10. The ammonia decomposition and hydrogen permeation reactor using magnetron sputtering coating technology according to claim 9, characterized in that It comprises a heating furnace (203), and the reactor is placed in the heating furnace (203).

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