CN112050202B - Tubular ammonia decomposition reactor - Google Patents
Tubular ammonia decomposition reactor Download PDFInfo
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- CN112050202B CN112050202B CN202010918430.7A CN202010918430A CN112050202B CN 112050202 B CN112050202 B CN 112050202B CN 202010918430 A CN202010918430 A CN 202010918430A CN 112050202 B CN112050202 B CN 112050202B
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN A CARRIER GAS OR AIR
- F23C13/00—Apparatus in which combustion takes place in the presence of catalytic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00504—Controlling the temperature by means of a burner
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- 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
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Abstract
The invention provides a tubular ammonia decomposition reactor, which comprises a sleeve and an inner tube arranged in the sleeve, wherein an ammonia decomposition catalyst is filled in the inner tube, and a catalytic combustion catalyst is filled in a gap between the inner tube and the sleeve. The fuel gas enters a gap between the inner tube and the sleeve from the second air inlet, generates heat under the action of the catalytic combustion catalyst, and discharges combustion waste gas from the second air outlet; ammonia gas enters the inner tube from the first air inlet, ammonia decomposition reaction is carried out under the action of an ammonia decomposition catalyst in the inner tube, and heat required in the reaction process is from catalytic combustion of fuel gas. Therefore, the device can carry out ammonia decomposition reaction only by filling the catalytic combustion catalyst in the gap between the inner pipe and the sleeve without additionally arranging heat generating devices such as a burner and the like, thereby effectively simplifying the structure of the device; meanwhile, in the later maintenance process of the equipment, only the catalytic combustion catalyst needs to be replaced, so that the difficulty and the workload of equipment maintenance are reduced.
Description
Technical Field
The invention relates to the technical field of ammonia decomposition hydrogen production, in particular to a tubular ammonia decomposition reactor.
Background
The ammonia decomposition hydrogen production is a chemical reaction, namely heating liquid ammonia to 800-850 ℃, and decomposing the ammonia under the action of a nickel-based catalyst to obtain the catalyst containing 75% of H 2 、25％N 2 Hydrogen-nitrogen mixed gas of (2). The raw material ammonia is easy to obtain, the price is low, and the raw material consumption is less. Therefore, hydrogen is supplied to the fuel cell by ammonia catalytic decomposition hydrogen production, which is an efficient and reliable way.
Chinese patent CN110203882a discloses an ammonia decomposing device, which comprises a housing, a reaction section and a heat exchange coil, wherein the housing comprises a heating zone and a heat exchange zone which are sequentially communicated; the reaction section comprises a first reaction section and a second reaction section which are sequentially communicated, the first reaction section is arranged in the heating zone, and the second reaction section is arranged in the heat exchange zone; the heat exchange coil is sequentially spirally wound on the outer walls of the second reaction section and the first reaction section. Wherein, a burner is arranged in the heating area and between the inner wall of the shell and the first reaction section, the fuel from the fuel tank enters the burner to burn, the generated heat is used for maintaining the reaction temperature in the first reaction section, and tail gas generated by combustion enters a heat exchange area and is used for preheating ammonia gas which does not enter the first reaction section for reaction; and maintaining the reaction temperature into the second reaction zone. However, the arrangement of the burner increases the structural complexity of the ammonia decomposition device, and the running cost of equipment and the difficulty of later equipment maintenance are also increased.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of complex structure and higher equipment operation cost of the existing ammonia decomposition device, thereby providing a tubular ammonia decomposition reactor.
To this end, the present invention provides a tubular ammonia decomposition reactor comprising:
the sleeve comprises a first air inlet, a first air outlet, a second air inlet and a second air outlet which are oppositely arranged;
the inner pipe is arranged in the sleeve, an ammonia decomposition catalyst is filled in the inner pipe, a catalytic combustion catalyst is filled in a gap between the inner pipe and the sleeve, one end of the inner pipe is communicated with the first air inlet, and the opposite end of the inner pipe is communicated with the first air outlet;
the second inlet port is adapted to communicate with a fuel gas adapted to react exothermically with the catalytic combustion catalyst.
Further, the first air inlet and the second air inlet are positioned at the same end of the tubular ammonia decomposition reactor, and the first air outlet and the second air outlet are positioned at the same end of the tubular ammonia decomposition reactor; or alternatively, the first and second heat exchangers may be,
the first air inlet and the second air inlet are positioned at the different ends of the tubular ammonia decomposition reactor, and the first air outlet and the second air outlet are positioned at the different ends of the tubular ammonia decomposition reactor.
Further, the inner tube comprises a plurality of parallel pipelines.
Further, the inner tube is a plurality of pipelines which are arranged in series.
Further, the inner tube includes
A plurality of first pipelines connected in parallel;
the air outlet mixing cavity is arranged between the catalytic combustion catalyst and the first air outlet, and the air outlet of the first pipeline enters the air outlet mixing cavity;
and one end of the second pipeline is connected in series, the other end of the second pipeline extends out of the area between the air outlet mixing cavity and the first air outlet, and the part between the two ends of the second pipeline is embedded into the catalytic combustion catalyst.
Further, the inner tube comprises a plurality of grooves,
a plurality of first pipelines connected in parallel;
the air inlet mixing cavity is arranged between the catalytic combustion catalyst and the first air inlet, and an air outlet of the first pipeline enters the air inlet mixing cavity;
and one end of the second pipeline is connected in series, the other end of the second pipeline extends out to the area between the air inlet mixing cavity and the first air inlet, and the part between the two ends of the second pipeline is embedded into the catalytic combustion catalyst.
Further, along the direction of gas flow, the ammonia decomposition catalyst in the inner tube is a first ammonia decomposition catalyst and a second ammonia decomposition catalyst in sequence, wherein the first ammonia decomposition catalyst is an Fe-based decomposition catalyst or an Ni-based decomposition catalyst, and the second ammonia decomposition catalyst is an Ru-based decomposition catalyst.
Further, the inner tube is filled with a plurality of layers of ammonia decomposition catalysts, wherein,
the particle size of the ammonia decomposition catalyst gradually decreases or gradually increases along the direction of gas flow, and the ratio of the particle size of the ammonia decomposition catalyst of the later layer to the particle size of the ammonia decomposition catalyst of the former layer is 0.25-4; and/or the number of the groups of groups,
the pore canal of the ammonia decomposition catalyst gradually decreases or gradually increases along the direction of gas flow, and the pore canal is 2nm-4000nm; and/or the number of the groups of groups,
the porosity of the ammonia decomposition catalyst gradually decreases or gradually increases along the direction of gas flow, and the porosity is 0.1-0.7.
Further, the catalytic combustion catalyst is a hydrogen catalytic combustion catalyst or an ammonia catalytic combustion catalyst, wherein the hydrogen catalytic combustion catalyst is MgAl 2 O 4 、Mn－Co－Cu－Fe－Ni/γ－Al 2 O 3 Cordierite, pt/gamma-Al 2 O 3 Cordierite or Pt/Ce x Zr 1－x O 2 /γ－Al 2 O 3 One or more of the ammonia catalytic combustion catalysts is Fe 2 O 3 、V 2 O 5 、Cr 2 O 3 MoOx or Wo x One or more of the following.
Further, the outer wall of the sleeve is provided with a heat insulation material.
Further, the tubular ammonia decomposition reactor further comprises a thermocouple penetrating through the outer wall of the sleeve.
The technical scheme of the invention has the following advantages:
1. the invention provides a tubular ammonia decomposition reactor, which comprises a sleeve and an inner tube arranged in the sleeve, wherein the sleeve comprises a first air inlet and a first air outlet, and a second air inlet and a second air outlet which are arranged oppositely, an ammonia decomposition catalyst is filled in the inner tube, a catalytic combustion catalyst is filled in a gap between the inner tube and the sleeve, one end of the inner tube is communicated with the first air inlet, the opposite end of the inner tube is communicated with the first air outlet, the second air inlet is suitable for being communicated with fuel gas, and the fuel gas is suitable for carrying out exothermic reaction with the catalytic combustion catalyst.
The fuel gas enters a gap between the inner tube and the sleeve from the second air inlet, generates heat under the action of the catalytic combustion catalyst, and discharges combustion waste gas from the second air outlet; ammonia enters the inner tube from the first air inlet, ammonia decomposition reaction is carried out under the action of an ammonia decomposition catalyst in the inner tube, and heat required in the reaction process is from catalytic combustion of fuel gas, so that the ammonia decomposition reaction can be carried out only by filling the catalytic combustion catalyst in the gap between the inner tube and the sleeve without arranging a heat generating device such as a burner and the like, thereby effectively simplifying the structure of the device and reducing the equipment cost; meanwhile, in the later maintenance process of the equipment, only the catalytic combustion catalyst needs to be replaced, so that the difficulty and the workload of equipment maintenance are reduced.
2. According to the tubular ammonia decomposition reactor provided by the invention, the gap between the inner tube and the sleeve is filled with the catalytic combustion catalyst to provide heat for the ammonia decomposition reaction, so that compared with a conventional thermal combustion method, the tubular ammonia decomposition reactor has the advantages of less auxiliary fuel required by catalytic combustion and low energy consumption, thus reducing the energy consumption required by the ammonia decomposition reaction and reducing the material cost of the ammonia decomposition reaction.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic structural view of a tubular ammonia decomposition reactor according to example 1 of the present invention;
FIG. 2 is a schematic structural view of a tubular ammonia decomposition reactor according to example 2 of the present invention;
FIG. 3 is a schematic structural view of a tubular ammonia decomposition reactor according to example 3 of the present invention;
FIG. 4 is a schematic structural view of a tubular ammonia decomposition reactor according to example 4 of the present invention;
reference numerals illustrate:
1-a sleeve; 11-a first air inlet; 12-a first air outlet; 121-a first sampling tube; 13-a second air inlet; 14-a second air outlet; 141-a second sampling tube; 2-an inner tube; 21-a first conduit; 22-a second conduit; 3-thermocouple; 4-a thermal insulation material; 5-grid plates; 6-upper partition plate; 61-a first upper separator; 62-a second upper separator; 7-a lower partition; 71-a first lower separator; 72-a second lower separator; 8-gas distributor; 9-an inlet flow meter; 10-outlet collector.
Detailed Description
The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. 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.
In the description of the present invention, it should be noted that the directions or positional relationships indicated by the terms "upper", "lower", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the apparatus or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
In addition, the technical features of the different embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Example 1
As shown in fig. 1, the present embodiment provides a tubular ammonia decomposition reactor comprising:
a sleeve 1 comprising a first air inlet 11 and a first air outlet 12, and a second air inlet 13 and a second air outlet 14 arranged opposite to each other;
the inner tube 2 is arranged in the sleeve 1, an ammonia decomposition catalyst is filled in the inner tube 2, a catalytic combustion catalyst is filled in a gap between the inner tube 2 and the sleeve 1, one end of the inner tube 2 is communicated with the first air inlet 11, and the opposite end is communicated with the first air outlet 12;
the second inlet 13 is adapted to communicate with a fuel gas adapted to react exothermically with the catalytic combustion catalyst.
In the tubular ammonia decomposition reactor, fuel gas enters a gap between the inner tube 2 and the sleeve 1 from the second air inlet 13, generates heat under the action of a catalytic combustion catalyst, and discharges combustion waste gas from the second air outlet 14; ammonia enters the inner tube 2 from the first air inlet 11, ammonia decomposition reaction is carried out under the action of an ammonia decomposition catalyst in the inner tube 2, and heat required in the reaction process is from catalytic combustion of fuel gas, so that the device can carry out ammonia decomposition reaction only by filling a catalytic combustion catalyst in a gap between the inner tube 2 and the sleeve 1 without additionally arranging a heat generating device such as a burner, thereby effectively simplifying the structure of the device and reducing the equipment cost; meanwhile, in the later maintenance process of the equipment, only the catalytic combustion catalyst needs to be replaced, so that the difficulty and the workload of equipment maintenance are reduced; in addition, the gap between the inner tube 2 and the sleeve 1 is filled with the catalytic combustion catalyst to provide heat for the ammonia decomposition reaction, so that compared with the conventional thermal combustion method, the auxiliary fuel required by the catalytic combustion is less, the energy consumption is low, the energy consumption required by the ammonia decomposition reaction is reduced, and the material cost of the ammonia decomposition reaction is reduced.
Further, the first air inlet 11 and the second air inlet 13 are positioned at the same end of the tubular ammonia decomposition reactor, and the first air outlet 12 and the second air outlet 14 are positioned at the same end of the tubular ammonia decomposition reactor. The sleeve 1 comprises an upper partition plate 6 and a lower partition plate 7 which are respectively abutted against the inner wall of the sleeve, wherein the upper partition plate 6 is arranged between the first air inlet 11 and the second air inlet 13, and the lower partition plate 7 is arranged between the first air outlet 12 and the second air outlet 14. The inner tube 2 comprises four parallel pipelines, and two ends of each pipeline respectively penetrate through the upper partition plate 6 and the lower partition plate 7, so that fuel gas enters the pipeline, ammonia gas enters a gap between the pipeline and the sleeve 1, and the mutual influence of two chemical reactions is ensured. It should be understood that the number of the first pipes 21 includes, but is not limited to, 4, and the shapes of the sleeve 1, the upper partition 6 and the lower partition 7 are not limited in this application, and may be selected as needed by those skilled in the art.
In order to ensure that the gas from the first gas inlet 11 is able to enter the respective ducts uniformly, a gas distributor 8 is provided at the end of the duct near the first gas inlet 11.
Further, the tubular ammonia decomposition reactor further comprises a grid plate 5 abutted against the inner wall of the sleeve 1, the grid plate 5 is arranged on one side, far away from the first air outlet 12, of the second air outlet 14, the catalytic combustion catalyst is arranged above the grid plate 5, and the inner tube 2 penetrates through the grid plate 5 so as to fix the inner tube 2. At the same time, the grid plate 5, the lower partition plate 7 and the inner wall of the sleeve 1 form a cavity, and the waste gas generated by the catalytic combustion of the fuel gas enters the cavity and is then discharged through the second air outlet 14.
As an alternative embodiment, the first air inlet 11 and the second air inlet 13 may also be disposed at opposite ends of the tubular ammonia decomposition reactor, and the first air outlet 12 and the second air outlet 14 are disposed at opposite ends of the tubular ammonia decomposition reactor, i.e. the second air outlet is on the same side as the first air inlet, and the second air inlet is on the same side as the first air outlet. The positions of the grid plate, the gas distributor, the upper partition plate and the lower partition plate are correspondingly adjusted.
Specifically, the fuel gas is hydrogen or ammonia, and the catalytic combustion catalyst is hydrogen catalytic combustion catalyst or ammonia catalytic combustion catalyst, wherein the hydrogen catalytic combustion catalyst is MgAl 2 O 4 、Mn－Co－Cu－Fe－Ni/γ－Al 2 O 3 Cordierite, pt/gamma-Al 2 O 3 Cordierite or Pt/Ce x Zr 1－x O 2 /γ－Al 2 O 3 One or more of (a) and (b) ammonia-catalyzed combustionThe catalyst is Fe 2 O 3 、V 2 O 5 、Cr 2 O 3 、MoO x Or Wo x One or more of the following.
The ammonia catalytic decomposition requires the absorption of heat, which results in a gradual decrease in temperature along the direction of ammonia flow. When the reactor is operated, a reaction-diffusion process occurs in the catalyst particles, a component concentration gradient exists in the catalyst particles due to the existence of the diffusion resistance of components in the particles, and when the diffusion resistance in the particles is greatly affected, reactant components cannot be effectively diffused into the catalyst particles, so that the utilization rate of the catalyst is reduced. The effect of the diffusion rate of components within the catalyst particles on the catalyst performance is typically expressed as an efficiency factor, which theoretical analysis shows generally monotonically decreases as the miller modulus increases. The factors such as the size of the catalyst particles, the pore canal size, the porosity, the ammonia decomposition conversion rate of the particle surface and the like all have influence on the Tile modulus, and the catalyst is specifically expressed as follows: as the catalyst particle size increases, the tim modulus increases; as the size of the pores in the particles increases, the tim modulus decreases; as the intra-particle porosity increases, the tim modulus decreases; in view of the above analysis, it is known that when the catalyst is loaded in the reactor, catalysts of different active components can be used in different regions, or catalysts of the same active components but different particle sizes, porosities or pore sizes can be used in different regions, so that the catalyst performance is adapted to the bed environment.
When the temperature span in the tubular ammonia decomposition reactor is large, in order to improve the utilization rate of the ammonia decomposition catalyst, the ammonia decomposition catalyst in the inner tube 2 is a first ammonia decomposition catalyst and a second ammonia decomposition catalyst in sequence along the flowing direction of ammonia, wherein the first ammonia decomposition catalyst is an Fe-based decomposition catalyst or an Ni-based decomposition catalyst, and the second ammonia decomposition catalyst is an Ru-based decomposition catalyst. This is because the reaction temperature of the Fe-based or Ni-based decomposition catalyst is about 850 ℃ and the reaction temperature of the Ru-based catalyst is about 500 ℃ so that the use temperature of the catalyst is adapted to the temperature in the tubular ammonia decomposition reactor, thereby improving the utilization rate of the ammonia decomposition catalyst. It should be understood that the filling manner of the first ammonia decomposition catalyst and the second ammonia decomposition catalyst may be adjusted as needed, and is not limited herein.
Further, in order to improve the ammonia decomposition efficiency, a plurality of layers of ammonia decomposition catalysts are arranged in the inner tube 2 along the flowing direction of the ammonia gas, and the applicable temperature of the ammonia decomposition catalysts is reduced layer by layer; for example, an iron-based medium-high temperature ammonia decomposition catalyst is filled near the air inlet end of the inner tube, a ruthenium-based medium-low temperature ammonia decomposition catalyst is filled near the air outlet end of the inner tube, and a nickel-based medium-temperature ammonia decomposition catalyst is filled between the two ammonia decomposition catalysts.
When the temperature span in the tubular ammonia decomposition reactor is small along the flowing direction of ammonia gas, the same catalyst, such as Ru-based decomposition catalyst, fe-based decomposition catalyst or Ni-based decomposition catalyst, can be used, and the purpose of improving the utilization rate of the catalyst is achieved by adjusting the particle sizes, pore channels and porosities of different catalyst layers in the pipeline. Specifically, the inner tube 2 is filled with a plurality of layers of ammonia decomposition catalysts, wherein the particle size of the ammonia decomposition catalysts gradually decreases or gradually increases along the direction of gas flow, and the ratio of the particle size of the ammonia decomposition catalyst of the later layer to the particle size of the ammonia decomposition catalyst of the former layer is 0.25-4; and/or the pore canal of the ammonia decomposition catalyst is gradually reduced or gradually increased along the direction of gas flow, and the pore canal is 2nm-4000nm; and/or the porosity of the ammonia decomposition catalyst gradually decreases or gradually increases along the direction of gas flow, the porosity being 0.1 to 0.7. It should be understood that the filling manner of the ammonia decomposition catalyst may be adjusted as needed, and is not limited herein.
In addition, in order to improve the ammonia decomposition efficiency, the particle sizes and/or pore channels and/or porosities of different catalyst layers in the pipeline can be adjusted, and meanwhile, the applicable temperature of each ammonia decomposition catalyst layer along the flowing direction of ammonia gas is reduced layer by layer, so that the self-heating ammonia decomposition reactor provided by the embodiment is suitable for different environments.
Specifically, the outer wall of the sleeve 1 is provided with the heat insulating material 4, so that the efficiency of outward diffusion of heat generated by catalytic combustion of fuel gas is reduced, and the heat utilization rate is improved.
Further, the tubular ammonia decomposition reactor also comprises a thermocouple 3 penetrating through the outer wall of the sleeve 1 for monitoring the temperature generated by the catalytic combustion catalyst, and then monitoring the normal running of the ammonia decomposition reaction.
Further, in order to detect the gas from the first gas outlet 12, a first sampling pipe 121 is provided at the first gas outlet 12; similarly, in order to detect the gas from the second gas outlet 14, a second sampling tube 141 is provided at the second gas outlet 14. In order to detect the flow of gas into the first gas inlet 11 and the second gas inlet 13, inlet flow meters 9 are provided at the first gas inlet 11 and the second gas inlet 13, respectively. In order to reduce the flow resistance, outlet collectors 10 are also provided at the first and second air outlets 12, 14.
Example 2
This example provides a tubular ammonia decomposition reactor which differs from the tubular ammonia decomposition reactor provided in example 1 only in that: as shown in fig. 2, the inner tube 2 is 5 pipelines arranged in series, one end of the inner tube 2 close to the first air inlet 11 penetrates through the upper partition plate 6, and one end of the inner tube 2 close to the first air outlet 12 penetrates through the lower partition plate 7, so that fuel gas enters the pipeline, ammonia gas enters a gap between the pipeline and the sleeve 1, and mutual influence of two chemical reactions is guaranteed. It should be understood that the number of the second pipes 22 includes, but is not limited to, 5, and the shapes of the sleeve 1, the upper partition 6 and the lower partition 7 are not limited in this application, and may be selected as needed by those skilled in the art.
Example 3
This example provides a tubular ammonia decomposition reactor which differs from the tubular ammonia decomposition reactor provided in example 1 only in that: as shown in fig. 3, the inner tube 2 includes:
4 first pipes 21 connected in parallel;
the air outlet mixing cavity is arranged between the catalytic combustion catalyst and the first air outlet 12, and the air outlet of the first pipeline 21 enters the air outlet mixing cavity;
and 2 second pipelines 22 connected in series, one end of each second pipeline enters the air outlet mixing cavity, the other end of each second pipeline extends out to the area between the air outlet mixing cavity and the first air outlet 12, and the part between the two ends of each second pipeline is embedded into the catalytic combustion catalyst.
Specifically, the lower partition 7 includes a first lower partition 71 and a second lower partition 72, where the first lower partition 71 is disposed near the grid 5, the second lower partition 72 is disposed near the first air outlet 12, the first pipe 21 penetrates through the first lower partition 71, one end of the second pipe 22 penetrates through the first lower partition 71, the opposite ends of the second pipe 22 sequentially penetrate through the first lower partition 71, the second lower partition 72, and the first lower partition 71, the second lower partition 72 and the inner wall of the sleeve 1 form an air outlet mixing chamber. After entering from the first air inlet 11, the ammonia gas sequentially enters the first pipeline 21, the mixing cavity and the second pipeline 22, and then is discharged from the first air outlet 12 through the opposite end of the second pipeline 22.
It is to be understood that the number of first pipes 21 includes, but is not limited to, 4, and the number of second pipes 22 includes, but is not limited to, 2, and those skilled in the art can select as desired. Meanwhile, the first pipeline 21 and the second pipeline 22 include, but are not limited to, the arrangement in sequence as shown in fig. 3, and the arrangement mode can be adjusted according to the needs.
Further, due to the low concentration of the reactant entering the second conduit 22, the second conduit 22 may use a more active ammonia decomposition catalyst relative to the first conduit 21 to more effectively treat the residual reactant from the first conduit 21, improving ammonia decomposition efficiency and making the reactor more compact. Meanwhile, compared with the arrangement mode of the inner tube 2 provided in embodiment 1 and embodiment 2, the arrangement mode of the inner tube 2 provided in this embodiment can more flexibly arrange the reaction tubes according to the requirements of catalyst performance and the like.
Example 4
This example provides a tubular ammonia decomposition reactor which differs from the tubular ammonia decomposition reactor provided in example 1 only in that: as shown in fig. 4, the inner tube 2 includes,
4 first pipes 21 connected in parallel;
an intake mixing chamber provided between the catalytic combustion catalyst and the first intake port 11, the intake port of the first duct 21 entering the intake mixing chamber;
and 2 second pipes 22, one ends of which enter the air inlet mixing cavity, and the other ends of which extend out to the area between the air inlet mixing cavity and the first air inlet 11, and the parts between the two ends of which are embedded into the catalytic combustion catalyst.
Specifically, the upper partition 6 includes a first upper partition 61 and a second upper partition 62, where the first upper partition 61 is disposed near the first air inlet 11, and the second lower partition 72 is disposed on a side of the first upper partition 61 facing away from the first air inlet 11, where the first pipe 21 penetrates through the second upper partition 62, one end of the second pipe 22 penetrates through the second upper partition 62, the other end of the second pipe 22 penetrates through the first upper partition 61 and the second upper partition 62 in sequence, and the first upper partition 61, the second upper partition 62 and the inner wall of the sleeve 1 form an air inlet mixing chamber. After entering from the first air inlet 11, the ammonia gas sequentially enters the second pipeline 22, the air inlet mixing cavity and the first pipeline 21, and then is discharged from the first air outlet 12 through the opposite end of the first pipeline 21.
It is to be understood that the number of first pipes 21 includes, but is not limited to, 4, and the number of second pipes 22 includes, but is not limited to, 2, and those skilled in the art can select as desired. Meanwhile, the first pipeline 21 and the second pipeline 22 include, but are not limited to, the arrangement in sequence as shown in fig. 3, and the arrangement mode can be adjusted according to the needs.
The concentration of the reactant gradually decreases along the flow direction, the corresponding reaction rate decreases, and the gas flow rate gradually increases, so that the arrangement mode of the inner tube 2 provided in this embodiment can properly reduce the downstream flow rate, increase the residence time, and facilitate the improvement of the conversion rate. Meanwhile, the arrangement of the inner tube 2 provided in this embodiment can more flexibly arrange the reaction tubes according to the catalyst performance, relative to the arrangement of the inner tube 2 provided in embodiments 1 and 2.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. A tubular ammonia decomposition reactor, comprising:
the sleeve (1) comprises a first air inlet (11) and a first air outlet (12) which are oppositely arranged, and a second air inlet (13) and a second air outlet (14) which are oppositely arranged;
an upper partition plate (6) which is positioned inside the sleeve (1) and is abutted against the inner wall of the sleeve (1), wherein the upper partition plate (6) separates a second air inlet (13) or a second air outlet (14) from a first air inlet (11);
the lower partition plate (7) is positioned inside the sleeve (1) and is abutted against the inner wall of the sleeve (1), and the lower partition plate (7) separates the second air outlet (14) or the second air inlet (13) from the first air outlet (12);
the inner tube (2) is arranged inside the sleeve (1) and between the upper partition plate (6) and the lower partition plate (7), an ammonia decomposition catalyst is filled in the inner tube (2), a catalytic combustion catalyst is filled in a gap between the inner tube (2) and the sleeve (1), an air inlet end of the inner tube (2) penetrates through the upper partition plate (6) and is communicated with the first air inlet (11), an air outlet end of the inner tube (2) penetrates through the lower partition plate (7) and is communicated with the first air outlet (12), the first air inlet is suitable for introducing ammonia gas, and the first air outlet is suitable for outputting hydrogen-nitrogen mixed gas;
the second inlet (13) is adapted to communicate with a fuel gas adapted to react exothermically with the catalytic combustion catalyst, and the second outlet is adapted to output combustion exhaust.
2. A tubular ammonia decomposition reactor according to claim 1, wherein the inner tube (2) comprises several parallel pipes.
3. A tubular ammonia decomposition reactor according to claim 1, wherein the inner tube (2) is a number of tubes arranged in series.
4. A tubular ammonia decomposition reactor according to claim 1, wherein the inner tube (2) comprises
A plurality of first pipelines (21) connected in parallel;
the air outlet mixing cavity is arranged between the catalytic combustion catalyst and the first air outlet (12), and the air outlet of the first pipeline (21) enters the air outlet mixing cavity;
and one end of the second pipeline (22) is connected in series, the other end of the second pipeline is connected into the air outlet mixing cavity, the other end of the second pipeline extends out to the area between the air outlet mixing cavity and the first air outlet (12), and the part between the two ends of the second pipeline is embedded into the catalytic combustion catalyst.
5. A tubular ammonia decomposition reactor according to claim 1, wherein the inner tube (2) comprises
A plurality of first pipelines (21) connected in parallel;
an intake mixing chamber provided between the catalytic combustion catalyst and the first intake port (11), the intake port of the first duct (21) entering into the intake mixing chamber;
and one end of the second pipeline (22) is connected in series, the other end of the second pipeline is connected into the air inlet mixing cavity, the other end of the second pipeline extends out to the area between the air inlet mixing cavity and the first air inlet (11), and the part between the two ends of the second pipeline is embedded into the catalytic combustion catalyst.
6. The tubular ammonia decomposition reactor according to any one of claims 1 to 5, wherein the ammonia decomposition catalyst in the inner tube (2) is a first ammonia decomposition catalyst and a second ammonia decomposition catalyst in this order in the direction of gas flow, wherein the first ammonia decomposition catalyst is an Fe-based decomposition catalyst or an Ni-based decomposition catalyst and the second ammonia decomposition catalyst is a Ru-based decomposition catalyst.
7. Tubular ammonia decomposition reactor according to any one of claims 1 to 5, wherein the inner tube (2) is filled with several layers of ammonia decomposition catalyst, wherein,
the particle size of the ammonia decomposition catalyst gradually decreases or gradually increases along the direction of gas flow, and the ratio of the particle size of the ammonia decomposition catalyst of the later layer to the particle size of the ammonia decomposition catalyst of the former layer is 0.25-4; and/or the number of the groups of groups,
the pore canal of the ammonia decomposition catalyst gradually decreases or gradually increases along the direction of gas flow, and the pore canal is 2nm-4000nm; and/or the number of the groups of groups,
the porosity of the ammonia decomposition catalyst gradually decreases or gradually increases along the direction of gas flow, and the porosity is 0.1-0.7.
8. The tubular ammonia decomposition reactor according to any one of claims 1 to 5, wherein the catalytic combustion catalyst is a hydrogen catalytic combustion catalyst or an ammonia catalytic combustion catalyst, wherein the hydrogen catalytic combustion catalyst is MgAl 2 O 4 、Mn－Co－Cu－Fe－Ni/γ－Al 2 O 3 Cordierite, pt/gamma-Al 2 O 3 Cordierite or Pt/Ce x Zr 1－x O 2 /γ－Al 2 O 3 One or more of the ammonia catalytic combustion catalysts is Fe 2 O 3 、V 2 O 5 、Cr 2 O 3 MoOx or Wo x One or more of the following.
9. A tubular ammonia decomposition reactor according to any one of claims 1-5, wherein the outer wall of the sleeve (1) is provided with a thermal insulation material (4).
10. A tubular ammonia decomposition reactor according to any one of claims 1 to 5, further comprising a thermocouple (3) extending through the outer wall of the sleeve (1).
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| CN115106049B (en) * | 2022-06-21 | 2023-07-18 | 福州大学 | Ammonia decomposition reactor with ammonia preheating function |
| CN115036539B (en) * | 2022-06-21 | 2024-01-23 | 福州大学 | Fuel cell power generation system and control method thereof |
| CN115090219B (en) * | 2022-07-31 | 2023-07-21 | 中国石油化工股份有限公司 | Hydrogen-ammonia mixed gas generating device and preparation method thereof |
| US20240166504A1 (en) * | 2022-11-21 | 2024-05-23 | Air Products And Chemicals, Inc. | Process and apparatus for cracking ammonia |
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