CN113451615A - Liquid ammonia cracking power generation system and method - Google Patents
Liquid ammonia cracking power generation system and method Download PDFInfo
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- CN113451615A CN113451615A CN202110541355.1A CN202110541355A CN113451615A CN 113451615 A CN113451615 A CN 113451615A CN 202110541355 A CN202110541355 A CN 202110541355A CN 113451615 A CN113451615 A CN 113451615A
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 289
- 238000005336 cracking Methods 0.000 title claims abstract description 35
- 238000010248 power generation Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 110
- 239000001257 hydrogen Substances 0.000 claims abstract description 83
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 83
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 239000012528 membrane Substances 0.000 claims abstract description 17
- 239000000446 fuel Substances 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 238000002485 combustion reaction Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 70
- 239000012530 fluid Substances 0.000 claims description 55
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000007084 catalytic combustion reaction Methods 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 3
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 230000000717 retained effect Effects 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims 1
- 230000005611 electricity Effects 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- OUFGXIPMNQFUES-UHFFFAOYSA-N molybdenum ruthenium Chemical compound [Mo].[Ru] OUFGXIPMNQFUES-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
- H01M8/0687—Reactant purification by the use of membranes or filters
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- 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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/30—Hydrogen technology
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Abstract
The invention discloses a liquid ammonia cracking power generation system, which comprises an ammonia decomposition furnace and a separator, wherein the ammonia decomposition furnace comprises an outer layer, an inner container and a buffer tank, the outer layer is a combustion chamber, the buffer tank is arranged above the inner container, and the inner container and the buffer tank are separated by a hydrogen permeable membrane; the outer layer of the ammonia decomposing furnace is not communicated with the inner container and the buffer tank respectively; the inner container is filled with ammonia decomposition catalyst. Liquid ammonia enters a decomposing furnace after being preheated to be catalytically decomposed, and the obtained hydrogen enters a buffer tank through a hydrogen permeable membrane, so that the balance and forward shift of the ammonia cracking reaction are promoted while the purification and separation of the hydrogen are realized. Part of hydrogen obtained by the reaction is subjected to catalytic oxidation to release heat to supply heat for the ammonia cracking reaction, and the rest part of hydrogen is introduced into a fuel cell to generate electricity. The system takes ammonia as a raw material to generate electricity, and realizes higher cracking conversion efficiency through the coupling of the hydrogen permeable membrane and the cracking reaction; the method for coating the catalyst on the inner wall of the device improves the heat exchange efficiency, reduces the volume of the system and simplifies the process.
Description
Technical Field
The invention relates to a liquid ammonia cracking power generation system and a method, belonging to the field of hydrogen production and storage.
Background
The liquid ammonia has high hydrogen content, easy transportation and low cost, and is an excellent hydrogen storage carrier. However, the liquid ammonia cracking reaction temperature is high, the heat absorption capacity is large, the liquid ammonia needs to be heated to 800-850 ℃ in an ammonia decomposition furnace generally, ammonia is decomposed under the action of a nickel-based catalyst, and the process requirement is high. In addition, in order to provide heat, fuel needs to be separately provided in the reaction process, so that the heat generated after the fuel is combusted is used for providing the heat required by the decomposition of ammonia, and further, the system is complex and high in cost.
Disclosure of Invention
Based on the technical problem, the invention provides a liquid ammonia cracking power generation system and a method.
The technical solution adopted by the invention is as follows:
a liquid ammonia cracking power generation system comprises an ammonia decomposition furnace and a separator, wherein the ammonia decomposition furnace comprises an outer layer, an inner container and a buffer tank, the outer layer is a combustion chamber, the inner container is arranged on the inner side of the outer layer, the buffer tank is arranged above the inner container, and the inner container and the buffer tank are separated by a hydrogen permeable membrane; the outer layer of the ammonia decomposing furnace is not communicated with the inner container and the buffer tank respectively; an ammonia decomposition catalyst is filled in the inner container;
a liquid ammonia conveying pipeline is connected with a liner raw material inlet of the ammonia decomposing furnace, a gas outlet of the buffer tank is connected with an inlet of the separator, the buffer tank is divided into two parts of gas by the separator, wherein one part of gas is discharged through an outlet of the first separator, and an outlet of the first separator is connected with the anode of the fuel cell through a first gas conveying pipeline; the other part of gas is discharged through an outlet of the second separator, and the outlet of the second separator is connected with an outer layer gas inlet of the ammonia decomposing furnace through a second gas conveying pipeline.
Preferably, the outer layer of the ammonia decomposing furnace is provided with a spiral airflow channel, and the inner wall of the spiral airflow channel is coated with a hydrogen catalytic combustion catalyst.
Preferably, the system also comprises a heat exchange device, wherein the heat exchange device comprises a first heat exchanger, a second heat exchanger, a third heat exchanger and a condenser, and the first heat exchanger, the second heat exchanger, the third heat exchanger and the condenser are respectively provided with a cold fluid inlet and a hot fluid outlet;
a cold fluid inlet of the first heat exchanger is connected with the liquid ammonia conveying pipeline, a cold fluid outlet of the first heat exchanger is connected with a cold fluid inlet of the second heat exchanger, a cold fluid outlet of the second heat exchanger is connected with a cold fluid inlet of the third heat exchanger, and a cold fluid outlet of the third heat exchanger is connected with a liner raw material inlet of the ammonia decomposing furnace;
a gas outlet of the liner of the ammonia decomposing furnace is connected with a hot fluid inlet of a second heat exchanger through a third gas conveying pipeline, a hot fluid outlet of the second heat exchanger is connected with a gas inlet of an ammonia catcher, and a gas outlet of the ammonia catcher is emptied;
the gas outlet of the buffer tank is connected with the hot fluid inlet of the first heat exchanger, and the hot fluid outlet of the first heat exchanger is connected with the inlet of the separator;
an outer layer gas outlet of the ammonia decomposing furnace is connected with a hot fluid inlet of a third heat exchanger, a hot fluid outlet of the third heat exchanger is connected with a hot fluid inlet of a condenser, a cold fluid inlet of the condenser is connected with a blower through an air conveying pipeline, and a cold fluid outlet of the condenser is connected with a first inlet of a mixer;
the second inlet of the mixer is connected with the second gas conveying pipeline, and the outlet of the mixer is connected with the gas inlet on the outer layer of the ammonia decomposing furnace.
Preferably, the inner wall of the hot fluid cavity of the third heat exchanger is also coated with a hydrogen catalytic combustion catalyst.
Preferably, the ammonia decomposition catalyst is a ruthenium-based catalyst, and the catalysis temperature is not higher than 600 ℃.
Preferably, the material of the hydrogen permeable membrane is palladium alloy or nickel alloy, and the hydrogen permeable membrane can work below 600 ℃.
Preferably, the hydrogen partial pressure in the ammonia decomposition furnace liner is higher than the hydrogen partial pressure in the buffer tank.
Preferably, the ammonia gas trap is filled with an ammonia gas adsorbent, and the ammonia gas adsorbent is activated carbon or a molecular sieve.
A liquid ammonia cracking power generation method adopts the system as above, and comprises the following steps:
(1) liquid ammonia raw materials are conveyed through a liquid ammonia conveying pipeline, the liquid ammonia raw materials are heated and vaporized through a first heat exchanger, a second heat exchanger and a third heat exchanger in sequence, and vaporized ammonia is conveyed to an ammonia decomposing furnace inner container;
(2) in the inner container of the ammonia decomposition furnace, ammonia is subjected to cracking reaction and decomposed into nitrogen and hydrogen, the obtained hydrogen enters a buffer tank through a hydrogen permeable membrane, the ammonia cracking reaction is promoted to be balanced and shifted forward while the hydrogen is purified and separated, and the rest impurity gases are retained in the inner container of the ammonia decomposition furnace;
(3) pure hydrogen in the buffer tank firstly enters a first heat exchanger to preheat liquid ammonia, then enters a separator and is divided into two parts, wherein one part of the pure hydrogen is conveyed to a fuel cell anode through an outlet of the first separator and a first gas conveying pipeline for reaction and power generation, the other part of the pure hydrogen is conveyed to a mixer through an outlet of the second separator and a second gas conveying pipeline, is mixed with air preheated by a condenser in the mixer and then is introduced into the outer layer of an ammonia decomposition furnace, and is further introduced into a third heat exchanger; in the flowing process, pure hydrogen is subjected to catalytic oxidation reaction to continuously provide heat for ammonia gas cracking reaction and liquid ammonia raw material preheating;
(4) the main component of impurity gas in the liner of the ammonia decomposition furnace is nitrogen and contains trace ammonia, the impurity gas enters the ammonia trap after being released by the second heat exchanger, and after the ammonia is trapped, the residual gas reaches the emission standard and is directly emptied.
Preferably, the method further comprises a system preheating step: a small amount of pure hydrogen and air are introduced into the outer layer of the ammonia decomposition furnace by using an air blower, a hydrogen catalytic combustion catalyst is coated on the outer layer of the ammonia decomposition furnace and the inner wall of the third heat exchanger, the pure hydrogen and oxygen are subjected to catalytic oxidation reaction near the wall surface, and the heat obtained by the reaction is preheated for the ammonia decomposition furnace and the third heat exchanger.
The beneficial technical effects of the invention are as follows:
the invention provides a liquid ammonia cracking power generation system and a method, wherein liquid ammonia is preheated and then enters an ammonia gas decomposing furnace to be catalytically decomposed, and the obtained hydrogen enters a buffer tank through a high-temperature hydrogen-permeable membrane, so that the balance and forward shift of an ammonia cracking reaction are promoted while the purification and separation of the hydrogen are realized; part of hydrogen obtained by the reaction is subjected to catalytic oxidation to release heat to supply heat for the ammonia cracking reaction, and the rest part of hydrogen is introduced into a fuel cell to generate electricity. The system takes ammonia as a raw material to generate electricity, and realizes higher cracking conversion efficiency through the coupling of the hydrogen permeable membrane and the cracking reaction. The method for coating the catalyst on the inner wall of the device improves the heat exchange efficiency, reduces the volume of the system and simplifies the process. In addition, the system and the method can directly generate power only by taking liquid ammonia and air as raw materials, and the product only contains nitrogen and water, so that the system and the method have the characteristics of cleanness and high efficiency.
Drawings
The invention will be further described with reference to the following detailed description and drawings:
fig. 1 is a schematic structural diagram of a liquid ammonia cracking power generation system according to the present invention.
Detailed Description
With the attached drawing, the liquid ammonia cracking power generation system comprises an ammonia decomposition furnace 1 and a separator 2, wherein the ammonia decomposition furnace 1 comprises an outer layer 101, an inner container 102 and a buffer tank 3, the outer layer is a combustion chamber, the inner container is arranged on the inner side of the outer layer, the buffer tank is arranged above the inner container, and the inner container and the buffer tank are separated by a hydrogen permeable membrane 4. The outer layer of the ammonia decomposing furnace is not communicated with the inner container and the buffer tank respectively; the inner container is filled with ammonia decomposition catalyst. The liquid ammonia conveying pipeline 5 is connected with an inner container raw material inlet of the ammonia decomposing furnace, a gas outlet of the buffer tank 3 is connected with an inlet of the separator 2, the gas is divided into two parts of gas through the separator 2, one part of the gas is discharged through an outlet of the first separator, and an outlet of the first separator is connected with an anode of the fuel cell 7 through the first gas conveying pipeline 6. The other part of the gas is discharged through a second separator outlet which is connected with a gas inlet on the outer layer of the ammonia decomposing furnace through a second gas conveying pipeline 8.
As a further design of the invention, the system also comprises a heat exchange device, wherein the heat exchange device comprises a first heat exchanger 9, a second heat exchanger 10, a third heat exchanger 11 and a condenser 12, and the first heat exchanger, the second heat exchanger, the third heat exchanger and the condenser are respectively provided with a cold fluid inlet and a hot fluid outlet. The cold fluid inlet of the first heat exchanger 9 is connected with the liquid ammonia conveying pipeline 5, the cold fluid outlet of the first heat exchanger is connected with the cold fluid inlet of the second heat exchanger 10, the cold fluid outlet of the second heat exchanger is connected with the cold fluid inlet of the third heat exchanger 11, and the cold fluid outlet of the third heat exchanger is connected with the inner container raw material inlet of the ammonia decomposing furnace. The gas outlet of the liner of the ammonia decomposing furnace is connected with the hot fluid inlet of the second heat exchanger through a third gas conveying pipeline 13, the hot fluid outlet of the second heat exchanger 10 is connected with the gas inlet of an ammonia catcher 14, and the gas outlet of the ammonia catcher is emptied. The gas outlet of the buffer tank 3 is connected with the hot fluid inlet of the first heat exchanger 9, and the hot fluid outlet of the first heat exchanger 9 is connected with the inlet of the separator 2. An outer layer gas outlet of the ammonia decomposing furnace is connected with a hot fluid inlet of a third heat exchanger 11, a hot fluid outlet of the third heat exchanger is connected with a hot fluid inlet of a condenser 12, a cold fluid inlet of the condenser is connected with an air blower 16 through an air conveying pipeline 15, and a cold fluid outlet of the condenser is connected with a first inlet of a mixer 17. The second inlet of the mixer 17 is connected with the second gas conveying pipeline 8, and the outlet of the mixer is connected with the gas inlet on the outer layer of the ammonia decomposing furnace.
Furthermore, the outer layer of the ammonia decomposing furnace is provided with a spiral airflow channel, namely, combustion gas enters the spiral airflow channel from the bottom of the outer layer, then spirally rises and is discharged from the top of the outer layer. The inner wall of the spiral gas flow channel is coated with a hydrogen catalytic combustion catalyst to improve the reaction conversion rate of pure hydrogen. The inner wall of the hot fluid cavity of the third heat exchanger 11 is also coated with a hydrogen catalytic combustion catalyst, and a small amount of unreacted pure hydrogen can continuously react in the third heat exchanger, so that the chemical energy of the hydrogen is fully utilized.
The hydrogen catalytic combustion catalyst can be selected from hydrogen catalytic combustion catalysts taking metals such as nickel, platinum, rhodium, cobalt and the like as active components. The ammonia decomposition catalyst can be ruthenium-based catalyst, and the catalysis temperature is not higher than 600 ℃. The hydrogen permeable membrane 4 is made of a palladium alloy or a nickel alloy and can operate at 600 ℃. The hydrogen partial pressure in the ammonia decomposition furnace liner is higher than that in the buffer tank. The ammonia gas trap 14 is filled with an ammonia gas adsorbent or an ammonia gas absorption liquid, and the ammonia gas adsorbent can be activated carbon or a molecular sieve.
The invention also provides a liquid ammonia cracking power generation method, which adopts the system and comprises the following steps:
(1) liquid ammonia raw materials are conveyed through a liquid ammonia conveying pipeline 5, the liquid ammonia raw materials are heated and vaporized through a first heat exchanger 9, a second heat exchanger 10 and a third heat exchanger 11 in sequence, and vaporized ammonia is conveyed to an inner container of an ammonia decomposing furnace 1.
(2) In the inner container of the ammonia decomposing furnace 1, ammonia is subjected to cracking reaction and decomposed into nitrogen and hydrogen, the obtained hydrogen enters the buffer tank 3 through the hydrogen permeable membrane 4, the ammonia cracking reaction is promoted to be balanced and shifted forward while hydrogen purification and separation are realized, and other impurity gases are left in the inner container of the ammonia decomposing furnace.
(3) Pure hydrogen in the buffer tank 3 firstly enters a first heat exchanger 9 to preheat liquid ammonia, then enters a separator 2 and is divided into two parts, one part of pure hydrogen is conveyed to a fuel cell 7 through a first separator outlet and a first gas conveying pipeline to perform anode reaction and generate power, the other part of pure hydrogen is conveyed to a mixer 17 through a second separator outlet and a second gas conveying pipeline, and the mixed pure hydrogen is mixed with air preheated by a condenser in the mixer and then is introduced into the outer layer of an ammonia decomposition furnace and further introduced into a third heat exchanger 11. In the flowing process, pure hydrogen is subjected to catalytic oxidation reaction to continuously provide heat for ammonia gas cracking reaction and liquid ammonia raw material preheating.
(4) The main component of the impurity gas in the inner container of the ammonia decomposing furnace 1 is nitrogen and contains trace ammonia, the impurity gas enters the second heat exchanger for heat release and then enters the ammonia catcher 14, and after the ammonia is caught, the residual gas reaches the emission standard and is directly emptied.
Further, the method also comprises a system preheating step: firstly, a small amount of pure hydrogen and air are introduced into the outer layer of the ammonia decomposition furnace by using the air blower 16, the inner walls of the outer layer of the ammonia decomposition furnace and the third heat exchanger are coated with a hydrogen catalytic combustion catalyst, the pure hydrogen and oxygen are subjected to catalytic oxidation reaction near the wall surface, and the heat obtained by the reaction is used for preheating the ammonia decomposition furnace and the third heat exchanger.
The invention is further illustrated by the following specific application examples:
a liquid ammonia cracking power generation system as shown in figure 1 is arranged in the ship, and the power requirement of navigation can be met by taking liquid ammonia as a raw material.
The specific implementation process is as follows:
a small amount of pure hydrogen and air are firstly introduced into the outer layer of the ammonia decomposition furnace by using a blower. The outer layer of the ammonia decomposition furnace and the inner wall of the third heat exchanger are coated with nickel-cobalt catalysts, pure hydrogen and oxygen are subjected to catalytic oxidation reaction near the wall surface, and the heat obtained by the reaction can be used for preheating the liquid ammonia decomposition furnace and the third heat exchanger.
After preheating is completed, liquid ammonia stored in the spherical tank is introduced into the liquid ammonia cracking power generation system by using a liquid pump. Liquid ammonia enters an inner container of the ammonia decomposition furnace after being preheated by the heat exchanger. The ruthenium-molybdenum catalyst is filled in the inner container of the ammonia decomposition furnace, and the working temperature is 550 ℃. Hydrogen obtained by the reaction enters the buffer tank through the hydrogen permeable membrane, and the rest impurity gas is left in the inner container of the ammonia decomposition furnace. Pure hydrogen in the buffer tank firstly enters a first heat exchanger to preheat liquid ammonia, then enters a separator and is divided into two parts, wherein one part of the pure hydrogen is introduced into a fuel cell anode for reaction and power generation, the other part of the pure hydrogen is introduced into a mixer, mixed with air, enters the outer layer of an ammonia decomposition furnace and is further introduced into a third heat exchanger. In the flowing process, pure hydrogen is subjected to catalytic oxidation reaction to continuously provide heat for ammonia gas cracking reaction and raw material preheating. The outer layer of the ammonia gas decomposing furnace is provided with a spiral flow passage, so that the reaction conversion rate of pure hydrogen is improved. A small amount of unreacted pure hydrogen can continue to react in the heat exchanger C, and the chemical energy of the hydrogen is fully utilized. The material flowing out of the hot fluid outlet of the exchanger C, still having a high temperature, is preheated for air while being cooled in the condenser. The main component of the gas obtained by cracking is nitrogen and contains trace ammonia. And introducing the mixed gas into a heat exchanger B to release heat, and then introducing the mixed gas into an ammonia catcher. After ammonia gas is trapped, the residual gas reaches the emission standard and is directly emptied.
Claims (10)
1. A liquid ammonia cracking power generation system, characterized in that: the ammonia decomposition furnace comprises an outer layer, an inner container and a buffer tank, wherein the outer layer is a combustion chamber, the inner container is arranged on the inner side of the outer layer, the buffer tank is arranged above the inner container, and the inner container and the buffer tank are separated by a hydrogen permeable membrane; the outer layer of the ammonia decomposing furnace is not communicated with the inner container and the buffer tank respectively; an ammonia decomposition catalyst is filled in the inner container;
a liquid ammonia conveying pipeline is connected with a liner raw material inlet of the ammonia decomposing furnace, a gas outlet of the buffer tank is connected with an inlet of the separator, the buffer tank is divided into two parts of gas by the separator, wherein one part of gas is discharged through an outlet of the first separator, and an outlet of the first separator is connected with the anode of the fuel cell through a first gas conveying pipeline; the other part of gas is discharged through an outlet of the second separator, and the outlet of the second separator is connected with an outer layer gas inlet of the ammonia decomposing furnace through a second gas conveying pipeline.
2. The liquid ammonia splitting power generation system of claim 1, wherein: the outer layer of the ammonia decomposing furnace is provided with a spiral airflow channel, and the inner wall of the spiral airflow channel is coated with a hydrogen catalytic combustion catalyst.
3. The liquid ammonia splitting power generation system of claim 1, wherein: the heat exchanger also comprises a heat exchange device, wherein the heat exchange device comprises a first heat exchanger, a second heat exchanger, a third heat exchanger and a condenser, and the first heat exchanger, the second heat exchanger, the third heat exchanger and the condenser are respectively provided with a cold fluid inlet and a hot fluid outlet;
a cold fluid inlet of the first heat exchanger is connected with the liquid ammonia conveying pipeline, a cold fluid outlet of the first heat exchanger is connected with a cold fluid inlet of the second heat exchanger, a cold fluid outlet of the second heat exchanger is connected with a cold fluid inlet of the third heat exchanger, and a cold fluid outlet of the third heat exchanger is connected with a liner raw material inlet of the ammonia decomposing furnace;
a gas outlet of the liner of the ammonia decomposing furnace is connected with a hot fluid inlet of a second heat exchanger through a third gas conveying pipeline, a hot fluid outlet of the second heat exchanger is connected with a gas inlet of an ammonia catcher, and a gas outlet of the ammonia catcher is emptied;
the gas outlet of the buffer tank is connected with the hot fluid inlet of the first heat exchanger, and the hot fluid outlet of the first heat exchanger is connected with the inlet of the separator;
an outer layer gas outlet of the ammonia decomposing furnace is connected with a hot fluid inlet of a third heat exchanger, a hot fluid outlet of the third heat exchanger is connected with a hot fluid inlet of a condenser, a cold fluid inlet of the condenser is connected with a blower through an air conveying pipeline, and a cold fluid outlet of the condenser is connected with a first inlet of a mixer;
the second inlet of the mixer is connected with the second gas conveying pipeline, and the outlet of the mixer is connected with the gas inlet on the outer layer of the ammonia decomposing furnace.
4. The liquid ammonia splitting power generation system of claim 1, wherein: the inner wall of the hot fluid cavity of the third heat exchanger is also coated with a hydrogen catalytic combustion catalyst.
5. The liquid ammonia splitting power generation system of claim 1, wherein: the ammonia decomposition catalyst is a ruthenium-based catalyst, and the catalysis temperature is not higher than 600 ℃.
6. The liquid ammonia splitting power generation system of claim 1, wherein: the material of the hydrogen permeable membrane is palladium alloy or nickel alloy, and the hydrogen permeable membrane can work below 600 ℃.
7. The liquid ammonia splitting power generation system of claim 1, wherein: the hydrogen partial pressure in the ammonia decomposition furnace liner is higher than that in the buffer tank.
8. The liquid ammonia splitting power generation system of claim 1, wherein: the ammonia trap is filled with an ammonia adsorbent, and the ammonia adsorbent is activated carbon or a molecular sieve.
9. A liquid ammonia cracking power generation method, using the system of any one of claims 1 to 8, characterized by comprising the steps of:
(1) liquid ammonia raw materials are conveyed through a liquid ammonia conveying pipeline, the liquid ammonia raw materials are heated and vaporized through a first heat exchanger, a second heat exchanger and a third heat exchanger in sequence, and vaporized ammonia is conveyed to an ammonia decomposing furnace inner container;
(2) in the inner container of the ammonia decomposition furnace, ammonia is subjected to cracking reaction and decomposed into nitrogen and hydrogen, the obtained hydrogen enters a buffer tank through a hydrogen permeable membrane, the ammonia cracking reaction is promoted to be balanced and shifted forward while the hydrogen is purified and separated, and the rest impurity gases are retained in the inner container of the ammonia decomposition furnace;
(3) pure hydrogen in the buffer tank firstly enters a first heat exchanger to preheat liquid ammonia, then enters a separator and is divided into two parts, wherein one part of the pure hydrogen is conveyed to a fuel cell anode through an outlet of the first separator and a first gas conveying pipeline for reaction and power generation, the other part of the pure hydrogen is conveyed to a mixer through an outlet of the second separator and a second gas conveying pipeline, is mixed with air preheated by a condenser in the mixer and then is introduced into the outer layer of an ammonia decomposition furnace, and is further introduced into a third heat exchanger; in the flowing process, pure hydrogen is subjected to catalytic oxidation reaction to continuously provide heat for ammonia gas cracking reaction and liquid ammonia raw material preheating;
(4) the main component of impurity gas in the liner of the ammonia decomposition furnace is nitrogen and contains trace ammonia, the impurity gas enters the ammonia trap after being released by the second heat exchanger, and after the ammonia is trapped, the residual gas reaches the emission standard and is directly emptied.
10. The method for generating power by liquid ammonia pyrolysis according to claim 9, further comprising a system preheating step of: a small amount of pure hydrogen and air are introduced into the outer layer of the ammonia decomposition furnace by using an air blower, a hydrogen catalytic combustion catalyst is coated on the outer layer of the ammonia decomposition furnace and the inner wall of the third heat exchanger, the pure hydrogen and oxygen are subjected to catalytic oxidation reaction near the wall surface, and the heat obtained by the reaction is preheated for the ammonia decomposition furnace and the third heat exchanger.
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