CN117383511A - Compact ammonia decomposition reaction device and ammonia decomposition hydrogen production system - Google Patents
Compact ammonia decomposition reaction device and ammonia decomposition hydrogen production system Download PDFInfo
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- CN117383511A CN117383511A CN202311679468.3A CN202311679468A CN117383511A CN 117383511 A CN117383511 A CN 117383511A CN 202311679468 A CN202311679468 A CN 202311679468A CN 117383511 A CN117383511 A CN 117383511A
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- ammonia decomposition
- ammonia
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- catalytic combustion
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 332
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 157
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 111
- 239000001257 hydrogen Substances 0.000 title claims abstract description 49
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 49
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 239000007789 gas Substances 0.000 claims abstract description 82
- 238000007084 catalytic combustion reaction Methods 0.000 claims abstract description 80
- 239000002994 raw material Substances 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 25
- 239000003546 flue gas Substances 0.000 claims description 25
- 238000005192 partition Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000004891 communication Methods 0.000 claims description 19
- 239000002737 fuel gas Substances 0.000 claims description 17
- 238000000746 purification Methods 0.000 claims description 17
- 230000006378 damage Effects 0.000 claims description 11
- 239000012530 fluid Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000003795 desorption Methods 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000001737 promoting effect Effects 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 239000000446 fuel Substances 0.000 description 20
- 238000002485 combustion reaction Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- -1 for example Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910020598 Co Fe Inorganic materials 0.000 description 1
- 229910002519 Co-Fe Inorganic materials 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical group 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/047—Decomposition of ammonia
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention relates to the field of ammonia decomposition hydrogen production, and discloses a compact ammonia decomposition reaction device and an ammonia decomposition hydrogen production system. The compact ammonia decomposition reaction device comprises a catalytic combustion unit, an ammonia decomposition unit and a raw material gas pipe. The catalytic combustion unit is provided with a first inner cavity, a catalytic combustion catalyst and a first air inlet and a first air outlet which are communicated with the first inner cavity. The ammonia decomposition unit is arranged at the inner side of the catalytic combustion unit and is provided with a second inner cavity, an ammonia decomposition catalyst and a second air outlet communicated with the second inner cavity. The raw material gas pipe is arranged at the inner side of the ammonia decomposition unit, the gas inlet end is provided with a second gas inlet, and the gas outlet end extends to the inner side of the ammonia decomposition unit and is communicated with the second inner cavity. Wherein, first air inlet and second air inlet set up the opposite both ends at compact ammonia decomposition reaction device. The invention integrates ammonia catalytic combustion, ammonia decomposition and raw material ammonia preheating, and reduces the occupied area of equipment.
Description
Technical Field
The invention belongs to the technical field of ammonia decomposition hydrogen production, and particularly relates to a compact ammonia decomposition reaction device and an ammonia decomposition hydrogen production system.
Background
Ammonia decomposition to produce hydrogen needs to be performed at high temperatures, with the heat source typically being electrical heating or fuel combustion. When electric heating is used as a heat source, the hydrogen production cost is high. When ammonia is used as fuel for combustion and heat supply, the laminar flow combustion speed and the heat value of the ammonia are low, the required ignition energy is high, the combustibility range is narrow, the continuous and stable combustion is difficult to ignite and realize, the ammonia combustion mechanism is ambiguous, and the design and the application of an ammonia burner are limited; when the ammonia-hydrogen mixed fuel is adopted, a part of the hydrogen which is burnt is uneconomical.
Disclosure of Invention
In order to solve the technical problems, the invention provides a compact ammonia decomposition reaction device and an ammonia decomposition hydrogen production system.
In a first aspect, the present invention provides a compact ammonia decomposition reaction device comprising a catalytic combustion unit, an ammonia decomposition unit, and a feed gas pipe. The catalytic combustion unit is provided with a first inner cavity, a catalytic combustion agent layer for promoting the fuel gas to perform oxidation exothermic reaction is arranged in the first inner cavity, and the catalytic combustion unit comprises a first air inlet and a first air outlet which are communicated with the first inner cavity. The ammonia decomposition unit is arranged on the inner side of the catalytic combustion unit and is provided with a second inner cavity, an ammonia decomposition catalyst layer is arranged in the second inner cavity, and the ammonia decomposition unit comprises a second air outlet communicated with the second inner cavity. The raw material gas pipe is arranged at the inner side of the ammonia decomposition unit, the gas inlet end of the raw material gas pipe is provided with a second gas inlet, and the gas outlet end of the raw material gas pipe extends to the inner side of the ammonia decomposition unit and is communicated with the second inner cavity. Wherein, first air inlet and second air inlet set up the opposite both ends at compact ammonia decomposition reaction device.
Specifically, the catalytic combustion unit comprises an upper part of a second pipe body and a first pipe body which are in fluid communication, a first air inlet is formed in the upper end of the second pipe body, a first air outlet is formed in the lower end of the first pipe body, and a catalytic combustion agent layer is arranged on the upper part of the second pipe body. The ammonia decomposition unit includes a lower portion of the second tube body, and the second inner chamber includes an inner chamber defined between the lower portion of the second tube body and the raw gas pipe. The compact ammonia decomposition reaction device further comprises a first partition plate arranged on the second pipe body, and the first partition plate divides the second pipe body into an upper part and a lower part which are not communicated with each other by fluid. The second pipe body is positioned on the inner side of the first pipe body, and the first inner cavity comprises an inner cavity defined by the upper part of the second pipe body and an inner cavity defined between the first pipe body and the second pipe body. Preferably, the side wall at the upper part of the second pipe body is provided with a plurality of communication holes communicated with the first pipe body.
Preferably, the catalytic combustion unit is provided with a number of baffles between the first and second tubes, the baffles being arranged to increase the flow path of the flue gas formed after catalytic combustion of the fuel gas.
Specifically, the ammonia decomposition unit is provided with a plurality of first pipelines positioned in the second inner cavity, the first pipelines are constructed in a spiral shape, and an ammonia decomposition catalyst layer is arranged in the first pipelines.
Specifically, the device further comprises a second partition plate and a third partition plate which are arranged in the second inner cavity, and the second partition plate and the third partition plate divide the second inner cavity into a first subchamber, a second subchamber and a third subchamber in sequence. The gas outlet end of the raw material gas pipe extends to the first subchamber, and a side hole is arranged on the side wall of the raw material gas pipe between the first baffle plate and the second baffle plate. The first pipeline is arranged in the second subchamber and communicated with the first subchamber and the third subchamber. The second air outlet is arranged at the part of the lower part of the second pipe body, which limits the third subchamber.
Further, the air heat exchange unit is arranged on the outer side of the catalytic combustion unit and is provided with a third inner cavity, the air heat exchange unit comprises a third air inlet and a third air outlet which are communicated with the third inner cavity, the third air inlet is close to the second air inlet, and the third air outlet is close to the first air inlet.
Specifically, the air heat exchange unit comprises a shell and a second pipeline, the shell is arranged on the outer side of the first pipe body, the upper end of the second pipe body protrudes out of the first pipe body, and the third inner cavity is defined by the upper portion of the second pipe body, the first pipe body and the shell. The compact ammonia decomposition reaction device further comprises a fourth baffle plate and a fifth baffle plate which are arranged in the third inner cavity, and the fourth baffle plate and the fifth baffle plate divide the third inner cavity into a fourth subchamber, a fifth subchamber and a sixth subchamber in sequence. The third air outlet is disposed in a portion of the housing defining a fourth subchamber. The second pipe is configured in a spiral shape, and the second pipe is arranged in the fifth subchamber and communicated with the fourth subchamber and the sixth subchamber. The third air inlet is provided in a portion of the housing defining the sixth subchamber.
In a second aspect, the present invention provides an ammonia decomposition hydrogen production system comprising a hydrogen purification system for purifying hydrogen in a reformed gas generated from the compact ammonia decomposition reaction device, and the compact ammonia decomposition reaction device of the first aspect. Wherein the fuel gas comprises ammonia and/or a stripping gas released from the hydrogen purification system.
Preferably, a temporary heater is further included for heating the ammonia gas entering the catalytic combustion unit to bring the catalytic combustion catalyst layer to a start-up temperature for ammonia catalytic combustion.
The invention has the characteristics and advantages that:
the compact ammonia decomposition reaction device integrates catalytic combustion, ammonia decomposition and raw material ammonia preheating, and further integrates air preheating, so that the occupied area of equipment is reduced. The catalytic combustion unit adopts catalytic combustion to replace ignition combustion, a burner is not required to be configured in the system, open flame does not exist in the reaction, and the combustion temperature is convenient to control. In addition, the flue gas generated by the catalytic combustion unit not only provides heat for the ammonia decomposition reaction, but also can preheat raw material ammonia and air, and equipment for preheating the raw material ammonia and air does not need to be independently arranged.
The ammonia decomposition hydrogen production system of the invention recycles the whole heat of the system, and the heat released by the flue gas can be maintained after the system normally operates without providing a heat source additionally.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a schematic view of a compact ammonia decomposition reaction device according to the present invention;
FIG. 2 shows a schematic diagram of an ammonia destruction hydrogen production system of the present invention.
Reference numerals illustrate:
100-compact ammonia decomposition reactor, 101-first baffle, 102-second baffle, 103-third baffle, 104-fourth baffle, 105-fifth baffle, 106-sixth baffle;
10-a catalytic combustion unit, 11-a first pipe body, 13-a baffle plate, 131-a first baffle plate, 132-a second baffle plate, 14-a catalytic combustion agent layer, 15-a communication hole, 16-a fuel air inlet pipe, 17-a first air inlet, 18-a flue gas outlet pipe and 19-a first air outlet;
20-ammonia decomposition unit, 21-second pipe body, 211-upper part of second pipe body, 212-lower part of second pipe body, 22-first subchamber, 23-second subchamber, 24-third subchamber, 25-first pipeline, 26-converted gas outlet pipe, 27-second gas outlet;
30-a raw material gas pipe, 32-a side hole and 33-a second gas inlet;
40-air heat exchange unit, 41-shell, 42-second pipeline, 43-air inlet pipe, 44-third air inlet, 45-air outlet pipe, 46-third air outlet, 47-fourth subchamber, 48-fifth subchamber and 49-sixth subchamber;
200-ammonia decomposition hydrogen production system, 210-electric heater, V01-first tank, V02-second tank, E01-first heat exchanger, E02-second heat exchanger, PSA-hydrogen purification system, C01-air compressor.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1, the present invention relates to a compact ammonia decomposition reaction device 100 including a catalytic combustion unit and an ammonia decomposition unit. The fuel gas is catalytically combusted in the catalytic combustion unit to release heat, the ammonia decomposition unit is heated, and the ammonia decomposition unit decomposes ammonia into H under the action of the ammonia decomposition catalyst 2 And N 2 . The fuel gas may be ammonia, hydrogen, desorption gas released from a hydrogen purification system, or the like. For convenience of distinction, ammonia gas used for catalytic combustion is referred to as fuel ammonia gas, and ammonia gas used for ammonia decomposition reaction is referred to as raw material ammonia gas.
Specifically, the compact ammonia decomposition reaction device 100 includes a catalytic combustion unit 10, an ammonia decomposition unit 20, and a raw gas pipe 30. The catalytic combustion unit 10 has a first interior cavity in which a catalytic combustion catalyst layer 14 for promoting an exothermic oxidation reaction of fuel gas is disposed, and the catalytic combustion unit 10 includes a first air inlet 17 and a first air outlet 19 in communication with the first interior cavity. The ammonia decomposition unit 20 is disposed inside the catalytic combustion unit 10 and has a second inner cavity in which an ammonia decomposition catalyst layer is disposed, and the ammonia decomposition unit 20 includes a second air outlet 27 communicating with the second inner cavity. The raw material gas pipe 30 is disposed inside the ammonia decomposition unit 20, one end (gas inlet end) of the raw material gas pipe 30 is provided with a second gas inlet 33, and the other end (gas outlet end) of the raw material gas pipe 30 extends to the inside of the ammonia decomposition unit 20 and is communicated with the second inner cavity. Wherein the first air inlet 17 and the second air inlet 33 are provided at opposite ends of the compact ammonia decomposition reaction device 100.
The fuel gas (such as fuel ammonia) and preheated air enter the first inner cavity of the catalytic combustion unit through the first air inlet 17, and under the action of the catalytic combustion catalyst layer 14, the fuel gas undergoes catalytic combustion reaction to generate a fuel gas containing N 2 And H 2 O flue gas and releases a lot of heat. Raw material ammonia gas enters the raw material gas pipe 30 through the second gas inlet 33, enters the second inner cavity of the ammonia decomposition unit 20 after absorbing heat and raising temperature, and is decomposed into H under the action of the ammonia decomposition catalyst layer 2 And N 2 Is a conversion gas of (a). Flow direction of flue gas in the catalytic combustion unit 10 and raw ammoniaThe flow direction in the raw material gas pipe 30 is opposite, and the flow direction of the flue gas is the same as the flow direction of the mixture gas in the ammonia decomposition unit 20. The compact ammonia decomposition reaction device 100 is arranged in such a way that the connection of external pipelines is facilitated, and the full heat exchange among units is facilitated.
More specifically, with continued reference to fig. 1, the compact ammonia decomposition reaction device 100 is provided with a first tube 11 and a second tube 21, both of which are extended in the longitudinal direction, wherein the second tube 21 is disposed inside the first tube 11. The second tubular body 21 comprises an upper portion and a lower portion which are not in fluid communication. Specifically, the second tube 21 has a first partition 101 therein dividing it into an upper portion and a lower portion, the upper portion 211 of the second tube and the lower portion 212 of the second tube being in fluid communication. The catalytic combustion unit 10 comprises an upper portion 211 of a second pipe body and a first pipe body 11 which are in fluid communication, a first air inlet 17 is arranged at the upper portion 211 of the second pipe body, a first air outlet 19 is arranged at the lower end of the first pipe body 11, and a catalytic combustion agent layer 14 is arranged at the upper portion 211 of the second pipe body. The first lumen includes a lumen defined by the upper portion 211 of the second tube and a lumen defined between the first tube 11 and the second tube 21. The inner cavity defined between the first tube 11 and the second tube 21 refers specifically to a space located inside the first tube 11 and located outside the second tube 21. The fuel gas enters the upper portion 211 of the second pipe body, and is oxidized with air by the catalytic combustion catalyst of the catalytic combustion catalyst layer 14 to generate flue gas and release a large amount of heat, and the generated flue gas flows into the first pipe body 11. Specifically, the catalytic combustion catalyst layer 14 includes two grid plates disposed in parallel and a catalytic combustion catalyst disposed between the two grid plates. More specifically, the grid plates are parallel to the cross section of the second tube body 21. The catalytic combustion catalyst is a metal compound or a noble metal, for example, platinum gauze or the like. The fuel gas may pass through the grid plate and contact the catalytic combustion catalyst, and a great deal of heat is released by the severe oxidation reaction at a temperature of about 800 ℃ and under normal pressure. The second lumen includes the lumen defined by the lower portion 212 of the second tube and the feed gas tube 30, i.e., the space within the lower portion 212 of the second tube and outside the feed gas tube 30.
In some embodiments, the catalytic combustion layer 14 is located at an end of the upper portion 211 of the second tubular body proximate the first air intake port 17. Preferably, the catalytic combustion catalyst layer 14 is spaced apart from the upper end of the second tube 21 such that the fuel gas and air enter the upper portion 211 of the second tube to be mixed before contacting the catalytic combustion catalyst layer 14. Alternatively, a mixing member for sufficiently mixing the fuel gas and the air may be provided at the upper port into the second pipe body 21. The mixing member may be a partition provided with a through hole; alternatively, the mixing member may be a tube body having one end opened and one end closed, and the side wall and/or the closed end of the tube body may be provided with a through hole communicating with the upper portion 211 of the second tube body.
In some embodiments, the side wall of the upper portion 211 of the second pipe body is provided with a plurality of communication holes 15 communicating with the first pipe body 11, the portion of the side wall being located inside the first pipe body 11. Specifically, the communication hole 15 is configured as a long hole extending in the axial direction of the second pipe body 21. More specifically, the plurality of communication holes 15 are arranged along the circumferential direction of the side wall of the second pipe body 21.
In some embodiments, a baffle 13 is disposed between the first tube 11 and the second tube 21, the baffle 13 being configured to increase the flow path of the flue gas, thereby increasing the heat exchange time of the flue gas with the material in the lower portion 212 of the second tube. Specifically, the baffle 13 includes a first baffle 131 and a second baffle 132 that are sequentially distributed in the axial direction. The first and second baffle plates 131 and 132 are configured as circular flat plates. The first baffle 131 is fixed to the outer side of the lower portion 212 of the second pipe body, and the outer diameter of the first baffle 131 is smaller than the inner diameter of the first pipe body 11, and the inner diameter of the first baffle 131 is about the outer diameter of the second pipe body. The second baffle 132 is fixed to the inner side of the first pipe 11, the outer diameter of the second baffle 132 is about the inner diameter of the first pipe 11, and the inner diameter of the second baffle 132 is smaller than the outer diameter of the second pipe. Referring to fig. 1, the flue gas alternately passes the outer side of the first deflector 131 and the inner side of the second deflector 132 in this order from top to bottom in the axial direction. Alternatively, the baffle 13 may also be configured in other forms that may increase the flow path.
In some embodiments, the upper end of the second tube 21 protrudes from the first tube 11, and the lower end of the second tube 21 is located inside the first tube 11. The raw material gas pipe 30 is configured as a cylindrical pipe body, one end of the raw material gas pipe 30 is disposed outside the lower end of the first pipe body 11, the raw material gas pipe 30 of this end is opened to a second gas inlet 33, and the other end of the raw material gas pipe 30 extends to the inside of the second pipe body 21. In some embodiments, the other end of the feed gas pipe 30 extends to the first baffle 101, and the side wall of the feed gas pipe 30 adjacent to one end of the first baffle 101 is provided with a side hole 32, through which side hole 32 the feed gas pipe 30 is in fluid communication with the lower portion 212 of the second pipe body.
In some embodiments, an ammonia decomposition catalyst layer is disposed within the lower portion 212 of the second tubular body. Specifically, the lower portion 212 of the second tube body is provided with a first pipe 25 located at the outer periphery of the raw gas pipe 30 (i.e., the first pipe 25 is provided in the second inner chamber), and the ammonia decomposition catalyst layer is provided in the first pipe 25. The catalyst within the ammonia decomposing catalyst layer may be Ni, ir, mo, co, pt, pd and Rh, as well as combinations of different metals such as Co-Mo, ni-Mo, fe-Mo, ni-Co, co-Mo-Fe-Ni-Cu, mg-Fe, fe-Co, ni-Fe, mg-Co-Fe, ni-Pt, ni-Pd, ir-Ni, cu-Zn, and Ru bimetallic components, and the like. Preferably, the first pipe 25 is constructed in a spiral shape, and the length of the first pipe 25 may be increased to allow the raw material ammonia gas to be sufficiently contacted with the ammonia decomposition catalyst to promote the ammonia decomposition reaction. More preferably, the first conduit 25 is coiled around the feed gas pipe 30. Optionally, a plurality of layers of first pipes 25 are arranged along the radial direction, and a plurality of first pipes 25 which are distributed in parallel and coiled along the circumferential direction are arranged on each layer; referring to fig. 1, for example, five layers of first pipes 25 are provided.
In some embodiments, the compact ammonia destruction reaction device 100 is provided with a second baffle 102 and a third baffle 103 positioned within the lower portion 212 of the second tubular body. The second partition 102 and the third partition 103 are axially distributed and divide the second inner chamber into a first sub-chamber 22, a second sub-chamber 23 and a third sub-chamber 24 which are sequentially distributed in the axial direction. Wherein the second barrier 102 and the first subchamber 22 are adjacent to the first barrier 101. The first pipe 25 is disposed in the second subchamber 23 and communicates with the first subchamber 22 and the third subchamber 24. The other end of the raw material gas pipe 30 extends to the first subchamber 22, the side hole 32 of the raw material gas pipe 30 is arranged on the side wall of the raw material gas pipe between the first baffle plate 101 and the second baffle plate 102, namely the raw material gas pipe 30 is connected with the first subchamber 2 through the side hole 322 are communicated. The second air outlet 27 is provided in a portion of the lower portion 212 of the second tubular body defining the third subchamber, i.e. the second air outlet 27 may be provided in the second tubular body 21, e.g. in a side wall or bottom wall, at the lower side of the third partition 103. Raw material ammonia gas is heated by a raw material gas pipe 30 and enters the first subchamber 22, flows along the first pipeline 25 after being continuously preheated in the first subchamber 22, contacts with the ammonia decomposition catalyst layer and is decomposed into H 2 And N 2 And then into the third subchamber 24 and out of the second air outlet 27. Before entering the ammonia decomposition unit 20, the raw ammonia gas is guided to a region (upstream region of the flue gas flow) in the catalytic combustion unit 10 where the flue gas temperature is highest through the raw ammonia gas pipe 30, so that the raw ammonia gas receives a part of the heat generated by the catalytic combustion reaction, and a temperature increase is obtained.
In some embodiments, the compact ammonia decomposition reaction device 100 further includes an air heat exchange unit 40, the air heat exchange unit 40 being disposed outside the catalytic combustion unit 10. The air heat exchange unit 40 has a third interior cavity, and the air heat exchange unit 40 includes a third air inlet 44 and a third air outlet 46 in communication with the third interior cavity. The air entering the catalytic combustion unit 10 may be preheated in the air heat exchange unit 40 and the air may absorb heat from the flue gas located in the catalytic combustion unit 10 in the air heat exchange unit 40. In a preferred embodiment, to increase the heat exchange efficiency, the air flow direction is opposite to the flue gas flow direction. Specifically, the third air inlet 44 is adjacent to the second air inlet 33, and the third air outlet 46 is adjacent to the first air inlet 17.
Specifically, the air heat exchange unit 40 includes a housing 41, the housing 41 is disposed outside the first tube 11, and the third inner cavity is defined at least by the housing 41 and the first tube 11. With continued reference to fig. 1, the third interior cavity is defined collectively by the upper portion 211 of the second tubular body, the first tubular body 11, and the outer shell 41. Both ends of the first pipe body 11 and the second pipe body 21 are positioned inside the housing 41, and one end (air inlet end) of the raw material air pipe 30 extends out of the housing 41. Preferably, the housing 41, the first tube 11, and the second tube 21 are coaxially disposed.
In some embodiments, the compact ammonia destruction reaction device 100 further includes a fourth baffle 104 and a fifth baffle 105 disposed in the third interior chamber. The fourth partition 104 and the fifth partition 105 are axially distributed and divide the third inner chamber into a fourth sub-chamber 47, a fifth sub-chamber 48 and a sixth sub-chamber 49 which are sequentially distributed in the axial direction. Wherein the fourth partition 104 and the fourth subchamber 47 are adjacent to the first partition 101. The third air outlet 46 is provided in a portion of the housing 41 defining a fourth subchamber 47, and the third air inlet 44 is provided in a portion of the housing 41 defining a sixth subchamber 49. The air heat exchange unit 40 further includes a second duct 42 provided to the fifth subchamber 48, and the second duct 42 communicates with the fourth subchamber 47, the sixth subchamber 49, respectively. Air to be heated enters the sixth subchamber 49 from the third air inlet 44, flows into the fourth subchamber 47 through the second conduit 42, and finally flows out of the third air outlet 46. Preferably, the second duct 42 is constructed in a spiral shape, and the length of the second duct 42 may be increased, thereby increasing the heat exchange period of the air. More preferably, the second pipe 42 is coiled around the first pipe body 11. Optionally, a plurality of layers of second conduits 42 are provided radially, and a plurality of parallel circumferentially coiled second conduits 42 are arranged per layer. Referring to fig. 1, for example, five layers of second pipes 42 are provided.
In some embodiments, the compact ammonia destruction reaction device 100 further includes a sixth baffle 106 disposed within the housing 41, the sixth baffle 106 dividing the third interior chamber into separate upper and lower portions. A fourth partition 104 and a fifth partition 105 are provided at the upper portion of the third inner chamber, which includes the fourth sub-chamber 47, the fifth sub-chamber 48, and the sixth sub-chamber 49, and which is the air heat exchange unit 40. The lower part of the third inner chamber is in communication with the first pipe body 11, the lower part of the third inner chamber belonging to the catalytic combustion unit 10. The first air outlet 19 is arranged at the bottom of the shell 41, and the flue gas flows into the lower part of the third inner cavity through the first pipe body 11 and then flows out of the first air outlet 19. Specifically, the sixth diaphragm 106 is constructed in a plate shape, the lower ends of the first pipe body 11 and the second pipe body 21 are flush, the sixth diaphragm 106 is connected to the lower ends of the first pipe body 11 and the second pipe body 21, and the raw material gas pipe 30 extends through the sixth diaphragm 106 into the second pipe body 21. The sixth partition 106 may be regarded as the bottom walls of the first and second tubes 11, 21, and the bottom wall of the air heat exchange unit 40. A sixth partition 106 aligned with the first pipe 11 is provided with an opening that allows the first pipe 11 to communicate with the lower portion of the third inner chamber.
With continued reference to FIG. 1, the catalytic combustion unit 10 further includes a fuel inlet conduit 16 and a flue gas outlet conduit 18 in communication with the first interior chamber. One end of the fuel intake pipe 16 is connected to the top of the second pipe body 21, and an opening at the other end of the fuel intake pipe 16 is the first intake port 17. One end of the flue gas outlet pipe 18 is connected to the bottom of the shell 41, and an opening at the other end of the flue gas outlet pipe is a first air outlet 19. The ammonia decomposition unit 20 further includes a reformed gas outlet pipe 26 communicating with the third subchamber 24, one end of the reformed gas outlet pipe 26 being connected to a bottom side wall of the lower portion 212 of the second pipe body, and the other end of the reformed gas outlet pipe 26 being open to the second gas outlet 27. The air heat exchanging unit 40 further includes an air inlet duct 43 and an air outlet duct 45 communicating with a sixth subchamber 49 at the upper part of the third inner chamber. One end of the air intake duct 43 is connected to a side wall of the housing 41 between the fifth partition 105 and the sixth partition 106, and the opening of the other end of the air intake duct 43 is the third air intake 44. One end of the air outlet pipe 45 is connected to the top of the housing 41, and the opening of the other end of the air outlet pipe 45 is a third air outlet 46.
It should be noted that the catalytic combustion unit 10 may not include the upper portion 211 of the second pipe body, and in this case, the ammonia decomposition unit 20 may include all the second pipe body 21. Alternatively, in some embodiments, the fuel intake pipe 16 is connected to the top of the first pipe body 11, the inner cavity of the first pipe body 11 is divided into two independent parts (top and lower), the catalytic combustion agent layer 14 is disposed on the top of the first pipe body 11, and the second pipe body 21 is located inside the lower portion of the first pipe body 11.
The compact ammonia decomposition reaction device 100 of the present invention integrates the catalytic combustion unit 10, the ammonia decomposition unit 20, and the air heat exchange unit, thereby reducing the floor space of the equipment. The catalytic combustion unit 10 adopts catalytic combustion instead of ignition combustion, a burner is not required to be configured in the system, open flame does not exist in the reaction, and the combustion temperature is convenient to control. In addition, the flue gas generated by the catalytic combustion unit 10 not only provides heat for the ammonia decomposition reaction, but also preheats the raw material ammonia gas and air,
the equipment for preheating the raw material ammonia gas and air is not required to be independently arranged.
Referring to FIG. 2, the present invention provides an ammonia destruction hydrogen production system 200 comprising the aforementioned compact ammonia destruction reaction apparatus 100 and a hydrogen purification system PSA. The PSA of the hydrogen purification system is a system for performing pressure swing adsorption purification on hydrogen in the conversion gas, and is used for adsorbing N in the conversion gas 2 And NH not participating in cleavage reaction 3 . The desorption gas of the PSA of the hydrogen purification system at least comprises N 2 、NH 3 And introducing hydrogen in a purging link of the PSA of the hydrogen purification system. In some embodiments, the stripping gas of the hydrogen purification system PSA further comprises hydrogen that remains unseparated in the hydrogen purification system PSA. In some embodiments, the fuel gas entering the compact ammonia destruction reaction device 100 also includes a desorption gas of the hydrogen purification system PSA.
In some embodiments, ammonia decomposition hydrogen production system 200 includes a first tank V01, a second tank V02, and an air compressor C01. The first tank V01 is used for storing liquid ammonia, and fuel ammonia and raw material ammonia are both derived from the liquid ammonia. The second tank V02 is used to store hydrogen produced by the ammonia destruction hydrogen production system 200.
Ammonia decomposition hydrogen production system 200 is described in detail below in conjunction with fig. 1 and 2. Air is compressed by the air compressor C01, enters the air heat exchange unit 40 of the compact ammonia decomposition reaction device 100 through the third air inlet 44 through a pipeline, and enters the catalytic combustion unit 10 of the compact ammonia decomposition reaction device 100 through the first air inlet 17 after being heated. A part of the liquid ammonia as fuel ammonia gas is also introduced from the first gas inlet 17 into the catalytic combustion unit 10 of the compact ammonia decomposition reaction device 100 as fuel ammonia gas and desorption gas. The air compressor C01 can be used for adjusting the ratio of fuel ammonia to air, and strictly controlling the concentration of ammonia entering the catalytic combustion unit 10 to be outside the explosion limit range, wherein the explosion limit range is 15% -30.2%.
The fuel ammonia gas, the desorption gas and the air are catalytically combusted in the catalytic combustion unit 10 to generate flue gas, and the flue gas provides heat for the ammonia decomposition reaction and is discharged from the first air outlet 19 in the form of tail gas out of the compact ammonia decomposition reaction device 100. In some embodiments, the tail gas is absorbed by the lye and then vented to the atmosphere. Part of the liquid ammonia is used as raw material ammonia, the raw material ammonia enters the raw material air pipe 30 from the second air inlet 33, and the raw material ammonia absorbs heat and enters the ammonia decomposition unit 20 to generate conversion gas after decomposition reaction. The converted gas flows out of the compact ammonia decomposition reaction device 100 from the second gas outlet 27, flows into the hydrogen purification system PSA through a pipeline to carry out hydrogen purification treatment, and the purified hydrogen flows into the second tank V02 to be stored. The ammonia decomposition and conversion adopts a low-temperature catalyst, the conversion reaction temperature is about 500 ℃, and the conversion pressure is 0.8-1.0 MPa. The catalytic combustion temperature can be controlled at 800 ℃, and the reaction pressure is 1.0-1.2 MPa.
In catalytic combustion, the activation temperature of ammonia is 390-400 ℃. In some embodiments, ammonia decomposition hydrogen production system 200 includes a heater 210, where heater 210 is configured to heat fuel ammonia during an initial stage of an ammonia decomposition hydrogen production process flow, where the heated fuel ammonia provides heat to catalytic combustor layer 14, causing the fuel ammonia to enter an ammonia catalytic combustion stage after the temperature of catalytic combustor layer 14 reaches an ammonia activation temperature. When the ammonia catalytic combustion phase is entered, the heater 210 may be deactivated, the heater 210 being used only to temporarily heat the fuel ammonia. Specifically, the heater 210 is an electric heater.
In some embodiments, ammonia decomposition hydrogen production system 200 further includes a first heat exchanger E01, a second heat exchanger E02. The first heat exchanger E01 is used for exchanging heat between the conversion gas and the liquid ammonia, and the liquid ammonia absorbs the heat of the conversion gas and then is divided into fuel ammonia and raw material ammonia, so that a part of heat can be obtained by the raw material ammonia entering the compact ammonia decomposition reaction device 100. The second heat exchanger E02 is a water cooler, and cools the reformed gas by using cooling water.
The ammonia decomposition hydrogen production system 200 of the invention fully recycles the heat of the system, and the heat released by the flue gas can be maintained after the system normally operates without providing a heat source additionally.
The foregoing is merely a few embodiments of the present invention and those skilled in the art may make various modifications or alterations to the embodiments of the present invention without departing from the spirit and scope of the invention in light of the present invention.
Claims (10)
1. A compact ammonia decomposition reaction device, comprising:
the catalytic combustion unit is provided with a first inner cavity, a catalytic combustion agent layer for promoting the fuel gas to perform oxidation exothermic reaction is arranged in the first inner cavity, the catalytic combustion unit comprises a first air inlet and a first air outlet which are communicated with the first inner cavity, and the catalytic combustion unit comprises an upper part of a second pipe body and a first pipe body which are in fluid communication;
the ammonia decomposition unit is arranged on the inner side of the catalytic combustion unit and is provided with a second inner cavity, an ammonia decomposition catalyst layer is arranged in the second inner cavity, the ammonia decomposition unit comprises a second air outlet communicated with the second inner cavity, and the ammonia decomposition unit comprises the lower part of a second pipe body; and
the raw material gas pipe is arranged at the inner side of the ammonia decomposition unit, the gas inlet end of the raw material gas pipe is provided with a second gas inlet, and the gas outlet end of the raw material gas pipe extends to the inner side of the ammonia decomposition unit and is communicated with the second inner cavity;
wherein the upper portion of the second tubular body and the lower portion of the second tubular body are not in fluid communication; the second pipe body is positioned at the inner side of the first pipe body, the first inner cavity comprises an inner cavity defined by the upper part of the second pipe body and an inner cavity defined between the first pipe body and the second pipe body, and the catalytic combustion agent layer is arranged at the upper part of the second pipe body; the second lumen includes a lumen defined between a lower portion of the second tube and the raw gas tube.
2. The compact ammonia destruction reaction device of claim 1, further comprising a first baffle disposed on the second tube, the first baffle separating the second tube into upper and lower portions that are not in fluid communication;
the first air inlet is arranged at the upper end of the second pipe body, and the first air outlet is arranged at the lower end of the first pipe body;
the first air inlet and the second air inlet are arranged at two opposite ends of the compact ammonia decomposition reaction device.
3. The compact ammonia decomposition reaction device according to claim 2, wherein a sidewall located at an upper portion of the second pipe body is provided with a plurality of communication holes communicating with the first pipe body.
4. A compact ammonia destruction reaction device according to claim 3, wherein the catalytic combustion unit is provided with baffles between the first and second tubes, the baffles being adapted to increase the flow path of the flue gas formed after catalytic combustion of the fuel gas.
5. The compact ammonia decomposition reaction device according to claim 4, wherein the ammonia decomposition unit is provided with a plurality of first pipes located in the second inner chamber, the first pipes being configured in a spiral shape, and an ammonia decomposition catalyst layer being provided in the first pipes.
6. The compact ammonia destruction reaction device of claim 5, further comprising a second baffle plate and a third baffle plate disposed in the second inner chamber, the second baffle plate and the third baffle plate being axially distributed and dividing the second inner chamber into a first subchamber, a second subchamber, and a third subchamber axially distributed;
the air outlet end of the raw material air pipe extends to the first subchamber, and a side hole is formed in the side wall of the raw material air pipe between the first partition plate and the second partition plate;
the first pipeline is arranged in the second subchamber and is communicated with the first subchamber and the third subchamber;
the second air outlet is arranged at the part of the lower part of the second pipe body, which limits the third subchamber.
7. The compact ammonia decomposition reaction device according to any one of claims 1 to 6, further comprising an air heat exchange unit disposed outside the catalytic combustion unit, the air heat exchange unit having a third inner cavity, the air heat exchange unit comprising a third air inlet and a third air outlet in communication with the third inner cavity,
wherein the third air inlet is close to the second air inlet, and the third air outlet is close to the first air inlet.
8. The compact ammonia decomposition reaction device according to claim 7, wherein the air heat exchange unit comprises a housing and a second pipe, the housing is provided outside the first pipe, an upper end of the second pipe protrudes from the first pipe, and the third inner cavity is defined by an upper portion of the second pipe, the first pipe, and the housing;
the compact ammonia decomposition reaction device further comprises a fourth baffle plate and a fifth baffle plate which are arranged in the third inner cavity, wherein the fourth baffle plate and the fifth baffle plate are axially distributed, and divide the third inner cavity into a fourth subchamber, a fifth subchamber and a sixth subchamber which are axially and sequentially distributed;
the third air outlet is arranged at the part of the fourth subchamber defined by the shell;
the second pipeline is configured to be spiral, is arranged in the fifth subchamber and is communicated with the fourth subchamber and the sixth subchamber;
the third air inlet is disposed in a portion of the sixth subchamber defined by the housing.
9. An ammonia decomposition hydrogen production system, characterized by comprising a hydrogen purification system and the compact ammonia decomposition reaction device according to any one of claims 1 to 8, wherein the hydrogen purification system is used for purifying and processing hydrogen in a conversion gas generated from the compact ammonia decomposition reaction device;
wherein the fuel gas comprises ammonia and/or a desorption gas released from the hydrogen purification system.
10. The ammonia decomposition hydrogen production system of claim 9 further comprising a temporary heater for heating ammonia entering said catalytic combustion unit to bring said catalytic combustion catalyst layer to an activation temperature for ammonia catalytic combustion.
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| CN217230245U (en) * | 2022-03-16 | 2022-08-19 | 青岛创启信德新能源科技有限公司 | Ammonia decomposition hydrogen production system |
| KR102482521B1 (en) * | 2021-12-21 | 2022-12-29 | 주식회사 씨이에스 | Ammonia decomposition reactor heating simultaneously the ammonia decomposition tube inside and outside |
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| FR1490186A (en) * | 1965-08-23 | 1967-07-28 | Allis Chalmers Mfg Co | Apparatus for the dissociation of ammonia |
| KR20110121821A (en) * | 2010-05-03 | 2011-11-09 | 한국지질자원연구원 | A micro-channel reactor for ammonia decomposition and ammonia decomposition method using the same |
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