CN115818666A - Normal-pressure ammonia production device and method based on plasma activation and chemical chain coupling - Google Patents
Normal-pressure ammonia production device and method based on plasma activation and chemical chain coupling Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 62
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 54
- 239000000126 substance Substances 0.000 title claims abstract description 36
- 230000008878 coupling Effects 0.000 title claims abstract description 27
- 238000010168 coupling process Methods 0.000 title claims abstract description 27
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 27
- 238000000678 plasma activation Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 378
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 176
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 82
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000001257 hydrogen Substances 0.000 claims abstract description 65
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 65
- 238000010521 absorption reaction Methods 0.000 claims abstract description 46
- 239000007787 solid Substances 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 38
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 26
- 239000010453 quartz Substances 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 238000005516 engineering process Methods 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000010248 power generation Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
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- 229910052751 metal Inorganic materials 0.000 claims description 5
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- 230000001174 ascending effect Effects 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000012806 monitoring device Methods 0.000 claims description 3
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- 238000010992 reflux Methods 0.000 claims description 2
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- 238000003786 synthesis reaction Methods 0.000 description 15
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- 230000008569 process Effects 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000009620 Haber process Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 238000007036 catalytic synthesis reaction Methods 0.000 description 2
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- 239000000446 fuel Substances 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- -1 Mn 5 N 2 Chemical class 0.000 description 1
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- 150000002829 nitrogen Chemical class 0.000 description 1
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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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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a normal pressure ammonia production device and method based on plasma activation and chemical chain coupling 2 Introducing and driving the plasma reactor to form a plasma jet reaction zone, inert N 2 High-activity nitrogen molecules mainly in a vibration excited state are formed through plasma activation. The plasma high-speed jet flow drives the nitrogen carrier to form a fluidized reaction zone to carry out high-efficiency nitrogen absorption reaction, gas/solid separation is realized through the cyclone separator, and the nitrogen carrier further enters the nitrogen release reactor to carry out nitrogen release reaction with electrolyzed hydrogen to generate high-purity ammonia. After the nitrogen releasing reaction is finished, the nitrogen carrier returns to the nitrogen plasma jet region to carry out the nitrogen absorbing reaction.The invention adopts plasma to realize N 2 The normal-pressure efficient activation utilizes the multi-stage reaction to realize N by virtue of the characteristics of low energy barrier, small by-product and circulation of nitrogen carrier in nitrogen absorption and release reaction regions in the chemical chain ammonia production reaction 2 And water to efficiently prepare high-purity ammonia gas.
Description
Technical Field
The invention relates to the technical field of ammonia production, in particular to a normal-pressure ammonia production device and method based on plasma activation and chemical chain coupling.
Background
Ammonia gas is not only an important chemical raw material and a good hydrogen carrier, but also can be used as a carrier of hydrogen gas in a modern energy system to store energy; the properties of carbon-free fuels are also attracting much attention. Ammonia gas is currently produced by the Haber-Bosch process, typically at temperatures of 400-600 ℃ and pressures of 200-400atm, and is carried out with catalysts, which also makes it the most energy intensive process in the chemical industry. The annual production of ammonia by the Haber-Bosch process is about 5 million tons, consuming 1-2% of the world's energy, using 3-5% of the world's natural gas production, emitting over 3 million tons of carbon dioxide annually. The harsh reaction conditions and the contradiction between thermodynamics and kinetics of the traditional Haber-Bosch process have prompted researchers to continuously strive for sustainable, environmentally friendly ammonia synthesis technologies.
The plasma synthesis of ammonia is a promising method capable of replacing the thermal catalysis synthesis of ammonia, the plasma technology can make the reaction difficult to carry out or slow in reaction rate under normal temperature and pressure, the reaction kinetics can be obviously enhanced, and the plasma technology is considered to be one of the most effective ways for destroying N = N triple bonds. The plasma jet is formed by ejecting plasma under the action of air flow and an electric field, so that the plasma can directionally flow in a working area to form a gas-solid fluidized reaction area, and the nitrogen fixation reaction efficiency is improved. The atmospheric pressure plasma jet can efficiently activate nitrogen under atmospheric pressure, and has the advantages of high electron temperature, convenient operation, simple structure and the like. The jet plasma reactor is driven by solar energy, clean power is utilized to provide electric energy, and green ammonia production is realized.
The renewable energy sources include hydrogen energy, wind energy, solar energy, geothermal energy and the like. Among them, hydrogen energy is considered to be the most promising energy source in the 21 st century. Water electrolysis is used as a hydrogen production method, and has the advantages of no pollution of products, no need of separation operation and capability of changing equipment along with hydrogen production capacity. The water electrolysis hydrogen production process can be divided into alkaline water electrolysis technology, solid polymer water electrolysis technology (SPEWE) and solid oxide water electrolysis technology (SOEC).
The development of the chemical chain technology provides a new idea for the ammonia synthesis process, the ammonia synthesis process is decoupled into 2 or more step reactions of nitrogen absorption and nitrogen release to produce ammonia, the contradiction between thermodynamics and kinetics of the ammonia synthesis can be well relieved, and competitive adsorption of reactants is avoided. Meanwhile, each step reaction can be optimized respectively, so that the whole chemical chain ammonia synthesis process can achieve the optimal reaction effect. Firstly, the nitrogen carrier and nitrogen gas are reacted in the nitrogen-absorbing reactor to complete the nitrogen-absorbing reaction, and then H in the nitrogen-releasing reactor is released 2 Carrying out hydrogenation nitrogen release reaction with a nitrogen carrier to generate NH 3 And simultaneously reducing the nitrogen carrier to an initial state. Compared with the traditional catalytic ammonia synthesis reaction, the chemical chain ammonia synthesis reaction can avoid N 2 And H 2 The problem of competing adsorption on the catalyst surface. In addition, the thermodynamics and kinetics of catalytic ammonia synthesis are contradictory, resulting in too slow reaction rate at low temperature and too high temperature to facilitate exothermic reaction. The chemical chain synthesis ammonia separately carries out the nitrogen absorption/release reaction, high-temperature nitrogen fixation can break through the higher thermodynamic strength of N = N triple bond, higher nitrogen fixation efficiency is ensured, the requirement of the nitrogen release reaction on temperature is not high, and simultaneously the NH can be relieved at relatively low temperature 3 Decomposition of NH in favor of 3 And (4) collecting. However, the traditional chemical chain synthesis ammonia technology has the defects of low nitrogen fixation rate, nitrogen absorption reaction and N 2 The requirement on the activation temperature condition is high, and the popularization of the chemical chain ammonia production technology is limited to a certain extent.
Disclosure of Invention
The invention aims to provide a normal-pressure ammonia production device and method based on plasma activation and chemical chain coupling, aiming at the defects of the prior art.
The purpose of the invention is realized by the following technical scheme: an atmospheric ammonia production device and method based on plasma activation and chemical chain coupling. The technical means adopted by the invention are as follows:
a device for preparing ammonia by coupling plasma jet with a chemical chain comprises a reactor, a supply system and a power supply;
the reactor comprises a plasma jet reactor, a nitrogen absorption reactor, a nitrogen release reactor and a water electrolysis hydrogen production reactor; the plasma jet reactor comprises a high-voltage electrode and a grounding electrode to form a plasma discharge area, and is connected with the nitrogen absorption reactor and used for activating nitrogen and sending the nitrogen to the nitrogen absorption reactor to react with a nitrogen carrier; the top of the nitrogen absorption reactor is communicated with a cyclone separator through a pipeline, a nitrogen carrier output port of the cyclone separator is connected with the nitrogen release reactor through a pipeline, and a feed back pipeline is also arranged between the lower part of the nitrogen release reactor and the nitrogen absorption reactor and is used for refluxing the nitrogen carrier reduced by the hydrogen; the water electrolysis hydrogen production reactor is connected with the nitrogen release reactor through a single-stage separator;
the supply system is connected with a flow control device and comprises a water vapor supply system and a nitrogen gas supply system, and the water vapor supply system is connected with the electrolytic cell reactor and is used for supplying water vapor for water electrolysis reaction; the nitrogen gas supply system is connected with the plasma jet reactor and is used for supplying nitrogen gas;
the power supply comprises a plasma power supply and a water electrolysis hydrogen production power supply; the plasma power supply is used for supplying power to the high-voltage electrode in the plasma jet reactor;
the water electrolysis hydrogen production power supply takes a new energy power generation mode which cannot be connected to the grid as a source, is used for supplying power for an electrochemical hydrogen evolution reaction in a water electrolysis hydrogen production reactor, and finally completes the preparation of ammonia gas under the normal pressure condition by taking nitrogen storage and discharge of a nitrogen carrier as a core and coupling a plasma technology.
Further, the reactor is connected with a temperature monitoring device.
Further, the water vapor supply system comprises a water pump, a water vapor generating device and a water vapor inlet valve, the water pump is used for supplying water to the water vapor generating device, and the generated water vapor enters the water electrolysis hydrogen production reactor through the water vapor inlet valve and the water vapor inlet pipe.
Further, the nitrogen gas supply system comprises a nitrogen gas bottle, a mass flow controller and a nitrogen gas valve, wherein the nitrogen gas bottle is used for storing nitrogen gas, and the mass flow controller and the nitrogen gas valve are used for controlling the flow of the nitrogen gas.
Further, the pulsating jet flow plasma reactor comprises an outer electrode, an inner electrode and N 2 The air inlet, the base, the material return pipe, the quartz cover and the air distribution plate are arranged on the base;
the outer electrode is of a hollow columnar structure, is fixed on the base and is connected with the low-voltage end of the plasma power supply; the inner electrode is arranged at the lower position in the hollow structure of the outer electrode and is integrally formed by a lower cylinder and an upper circular table, the bottom of the inner electrode is fixed on the base and is connected with the high-voltage end of the plasma power supply through an electrode lead sheet penetrating through the base; the outer wall of the inner electrode is parallel to the inner wall of the outer electrode;
the wall surface of the outer electrode is provided with two paths of N with the same height 2 Wind inlet, two paths N 2 The air inlet is oppositely flushed to tangentially intake air, so that the introduced N is 2 A spirally rising gas flow is formed in the gap between the inner electrode and the outer electrode.
Further, the nitrogen-absorbing reactor includes: the device comprises a material return pipe, a quartz cover and an air distribution plate;
the quartz cover is fixed at the top of the outer electrode and is provided with a temperature control device; the air distribution plate is transversely fixed on the inner wall of the bottom of the quartz cover; the top of the quartz cover is communicated with the cyclone separator through a pipeline, the nitrogen carrier output port of the cyclone separator is connected with the nitrogen release reactor through a pipeline, and the nitrogen carrier reduced to the initial state by hydrogen is communicated with the feed back port of the quartz cover through the feed back pipeline of the nitrogen release reactor.
Furthermore, the nitrogen carrier is a metal nitrogen carrier and is used for matching the temperature of the pulsating jet flow plasma reactor, the downstream heat of the pulsating jet flow plasma reactor is used as a heat source of a nitrogen absorption reaction zone, fe and Mn with nitrides in various valence states are used as nitrogen carriers, and nitrogen fixation reaction is carried out at 700-900 ℃.
Further, the power supply for hydrogen production by water electrolysis is a direct-current power supply device, wherein one end of a negative electrode wire is connected with a hydrogen evolution electrode of the electrolytic cell, and the other end of the negative electrode wire is connected with a negative electrode of the direct-current power supply; one end of the positive wire is connected with the oxygen evolution electrode of the electrolytic cell, and the other end is connected with the positive electrode of the direct current power supply.
Further, the water electrolysis hydrogen production reactor is a solid polymer electrolytic cell reaction chamber or a solid oxide electrolytic cell reaction chamber.
According to a second aspect of the present description, there is provided a method of ammonia production by coupling a plasma jet with a chemical chain, the method comprising:
opening a steam inlet valve to inject steam into the solid polymer electrolytic cell reactor or the solid oxide electrolytic cell reaction chamber through a steam inlet pipe;
the water vapor is electrolyzed in an electrolytic cell to generate hydrogen and oxygen, the oxygen is discharged after passing through a single-stage separator, the hydrogen enters a nitrogen release reactor through a conveying pipe after being pressurized by a centrifugal pump, and the hydrogen generated in the hydrogen enters the nitrogen release reactor through a gas conveying pipeline after passing through the single-stage separator;
the nitrogen carrier which completes the nitrogen absorption reaction in the nitrogen absorption reactor enters a cyclone separator through a pipeline to complete the separation of the nitrogen carrier and nitrogen, the separated nitrogen carrier enters a nitrogen release reactor to contact with hydrogen which enters a reaction chamber through a gas pipeline and to generate hydrogen absorption and nitrogen release reactions, ammonia gas is generated, and meanwhile, the nitrogen carrier is returned to the nitrogen absorption reactor through a material return pipeline for circulation after being reduced to an initial state.
The invention has the beneficial effects that:
the method has zero carbon emission in the whole ammonia production process, and the plasma jet and the solid oxide electrolytic cell or the solid polymer electrolytic cell do not generate any carbon emission in the working process.
The method utilizes chemical chains to synthesize NH 3 Meanwhile, the nitrogen carrier is reduced to an initial state, and compared with the traditional catalytic ammonia synthesis reaction, the chemical-looping ammonia synthesis reaction can avoid N 2 And H 2 Competing for adsorption on the catalyst surface. In addition, the method solves the thermodynamic and kinetic contradiction of catalytic synthesis of ammonia, improves the problems that the reaction rate is too slow at low temperature and the excessive temperature is not beneficial to the heat release reaction, ensures higher nitrogen fixation efficiency and relieves NH 3 Decomposition of NH in favor of 3 And (4) collecting.
The jet plasma breaks through the kinetic barrier of thermochemical reaction through the action of high-energy electrons and active particles, and the N is converted under the condition of not depending on a catalyst 2 Conversion of molecules to highly active, excited N 2 Molecular, highly active, excited state N 2 The molecule can form nitride-carrying nitrogen with common metals, such as Mn 5 N 2 、Fe 4 N, crN, etc. And the efficient nitrogen fixation reaction is performed at a corresponding temperature, so that the reaction efficiency is improved.
The jet plasma generating source separates the discharge generating area from the reaction area, so that the discharge stability and the reaction area are not interfered and limited mutually, and the jet plasma generating source is favorable for practical application.
The gas flow velocity of the plasma jet flow is high, and the formed gas-solid fluidized reaction zone can lead the high-reactivity N to pass through the strong heat and mass transfer characteristic of the fluidized state 2 The plasma is in sufficient contact with the nitrogen carrier and reacts.
The downstream heat of the jet plasma reactor can be used as a heat source of a nitrogen absorption reaction area, and maintains reasonable temperature by matching with a temperature controller, so that the investment of an industrial process is reduced, and the actual application is facilitated. Taking metal nitrogen carrier as an example, fe with low price and excellent performance and Mn with nitrides in various valence states are taken as nitrogen carriers, nitrogen fixation reaction can be carried out at 700-900 ℃, heat required by the reaction can be provided by waste heat at the downstream of a jet plasma reactor, and the energy utilization rate is improved.
The plasma technology is coupled with the chemical chain technology, and the nitrogen carrier is recycled. After the nitrogen carrier is subjected to hydrogenation and nitrogen release reaction, the nitrogen carrier reduced to the initial state is returned to the nitrogen absorption reaction zone through the material return pipeline for nitridation again for circulation, so that the investment in the chemical-looping ammonia preparation process is reduced, the waste in the industrial process is reduced, and the practical application is facilitated.
The electric energy required by the jet plasma reactor and the electrolyzed water hydrogen production reactor is provided by solar power generation, and the energy is supplied by green clean energy, so that the carbon emission is zero when the whole system device is used for producing ammonia.
Drawings
FIG. 1 is a schematic diagram of the structure and molecular reaction diagram of a plasma activated and chemical looping coupled high efficiency ammonia production system reactor of the present invention;
FIG. 2 is a flow chart of the plasma activation and chemical looping coupled high efficiency ammonia process of the present invention.
In the figure: 1. a first check valve; 2. a first flow controller; 3. a first centrifugal pump; 4. a base; 5. an inner electrode; 6. an outer electrode; 7. a flange; 8. a nitrogen absorption reactor; 9. a quartz cover; 10. a cyclone separator; 11. a nitrogen release reactor; 12. a second centrifugal pump; 13. a second flow controller; 14. a plasma jet reactor; 15. a single stage separator; 16. a water electrolysis hydrogen production reactor; 17. a heater; 18. a third flow controller; 19. a water pump; 20. a third centrifugal pump; 21. a fourth flow controller; 22. a second check valve; 23. a heating furnace cover; 24. a wind distribution plate; 25. a feed back pipeline.
Detailed Description
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
As shown in fig. 1-2, the embodiment of the invention discloses a high-efficiency ammonia production device and method based on plasma activation and chemical chain coupling, wherein the device comprises a reactor, a supply system and a power supply;
the reactors comprise a plasma jet reactor 14, a nitrogen absorption reactor 8, a nitrogen release reactor 11 and a water electrolysis hydrogen production reactor 16; and the reactors are all connected with a temperature monitoring device.
The plasma jet reactor 14 comprises a high voltage electrode and a grounding electrode, a plasma discharge area is formed,
the pulsating jet plasma reactor 14 is connected with the nitrogen absorption reactor 8 and is used for activating nitrogen and sending the nitrogen to the nitrogen absorption reactor 8 to react with a nitrogen carrier; the pulsating jet plasma reactor comprises an outer electrode 6, an inner electrode 5 and N 2 An air inlet, a base 4;
the outer electrode 6 is a hollow columnar structure, is fixed on the base 4 and is connected with the low-voltage end of the plasma power supply; the inner electrode 5 is arranged at the middle lower position of the hollow structure of the outer electrode 6 and is integrally formed by a lower cylinder and an upper circular table, the bottom of the inner electrode 5 is fixed on the base 4 and is connected with the high-voltage end of a plasma power supply through an electrode lead sheet penetrating through the base 4; the outer wall of the inner electrode 5 is parallel to the inner wall of the outer electrode 6;
the wall surface of the outer electrode 6 is provided with two paths of N with the same height 2 Wind inlet, two ways N 2 The air inlet is oppositely flushed to tangentially intake air, so that the introduced N is 2 A spirally rising gas flow is formed in the gap between the inner electrode 5 and the outer electrode 6.
The nitrogen-adsorbing reactor 8 includes: a feed back pipeline 25, a quartz cover 9 and an air distribution plate 24; the quartz cover 9 is fixed on the top of the outer electrode 6 through a flange 7, and the air distribution plate 24 is transversely fixed on the inner wall of the bottom of the quartz cover 9; the top of the quartz cover 9 is communicated with a cyclone separator 10 through a pipeline, the nitrogen carrier output port of the cyclone separator 10 is connected with a nitrogen release reactor 11 through a pipeline, and the nitrogen carrier reduced to the initial state by hydrogen is communicated with a feed back port of the quartz cover 9 through the nitrogen release reactor 11 and a feed back pipeline 25;
the water electrolysis hydrogen production reactor 16 is a solid polymer electrolytic cell (SPEWE) reaction chamber or a Solid Oxide Electrolytic Cell (SOEC) reaction chamber; the solid polymer type water electrolyzer has a working temperature of 60-100 deg.C, has the same structure as fuel cell, and is composed of electrolyte membrane-electrode assembly (MEA). The electrolyte membrane generally uses a cation exchange membrane of 100-300 um and has an excellent gas separation function.
The water electrolysis hydrogen production reactor 16 is connected with the single-stage separator 15, the second flow controller 13, the second centrifugal pump 12 and the nitrogen release reactor 11 in sequence; the single-stage separator 15 is provided with an oxygen outlet pipe and a hydrogen outlet pipe, the hydrogen outlet pipe is connected with the nitrogen release reactor 11, the oxygen outlet pipe discharges oxygen,
the supply system is connected with a flow control device and comprises a water vapor supply system and a nitrogen gas supply system,
the water vapor supply system is used for supplying water vapor for water electrolysis reaction; the water vapor supply system comprises a water pump 19, a water vapor generating device (heater 17) and a third flow controller 18, the water pump 19 is connected with the heater 17 through the third flow controller 18 and supplies water, and the water vapor generated by the heater 17 enters the water electrolysis hydrogen production reactor 16 through a water vapor inlet valve and a water vapor inlet pipe.
The nitrogen gas supply system is connected with the plasma jet reactor 14 and is used for supplying nitrogen gas; the nitrogen gas supply system in the embodiment comprises a nitrogen gas cylinder, a first check valve 1, a first flow controller 2, a first centrifugal pump 3, a third centrifugal pump 20, a fourth flow controller 21 and a second check valve 22
The nitrogen cylinder is used for storing nitrogen, and the first check valve 1, the first flow controller 2 and the first centrifugal pump 3 are connected with each other and used for controlling the flow of the nitrogen. The third centrifugal pump 20, the fourth flow controller 21 and the second check valve 22 are also connected with each other to control the flow,the first centrifugal pump 3 and the third centrifugal pump 20 are respectively connected with two paths of N with the same height arranged on the wall surface of the outer electrode 6 2 An air inlet; the first check valve 1 and the second check valve 22 are respectively connected with different nitrogen bottles;
the power supply comprises a plasma power supply and a water electrolysis hydrogen production power supply; the plasma power supply is used for supplying power to the high-voltage electrode in the plasma jet reactor 14;
the water electrolysis hydrogen production power supply takes a new energy power generation mode (such as photovoltaic power generation and wind power generation) which cannot be connected to the grid as a source, is used for supplying power for an electrochemical hydrogen evolution reaction in the water electrolysis hydrogen production reactor 16, and finally completes the preparation of ammonia gas under the normal pressure condition by taking nitrogen storage and discharge of a nitrogen carrier as a core and coupling a plasma technology. The water electrolysis hydrogen production power supply is a direct current power supply device, wherein one end of a negative electrode wire is connected with a hydrogen evolution electrode of the water electrolysis hydrogen production reactor 16, and the other end of the negative electrode wire is connected with a negative electrode of the direct current power supply; one end of the positive electrode line is connected with the oxygen precipitation electrode of the water electrolysis hydrogen production reactor 16, and the other end is connected with the positive electrode of the direct current power supply.
In the embodiment, the temperature control device comprises a heating furnace cover 23, a temperature controller is connected with a quartz cover 9 which surrounds the outer surface of the reactor, so that the temperature in the nitrogen absorption reaction chamber is kept at 700-900 ℃, and the temperature value is monitored.
In the embodiment, the metal nitrogen carrier is used as the nitrogen carrier to circulate in the chemical chain process, the nitrogen fixation reaction can occur at 700-900 ℃, and the heat required by the nitrogen absorption reaction is provided by the downstream heat of the jet plasma reactor and the heating furnace cover 23.
The embodiment of the invention also provides a high-efficiency ammonia preparation method based on plasma activation and chemical chain coupling, which comprises the following steps:
Me x N y-1 +1/2N 2 (v)＝Me x N y
the micro jet flow provides high-speed airflow for the nitrogen carrier to form a gas-solid fluidized reaction zone, activated excited nitrogen gas and the nitrogen carrier generate high-efficiency nitrogen fixation reaction, the nitrogenized nitrogen carrier enters a nitrogen release reactor 11 after being treated by a cyclone separator 10, and reacts with hydrogen gas to generate ammonia gas after being treated by a gas separation device; the reaction is as follows:
Me x N y +3/2H 2 ＝Me x N y-1 +NH 3 。
the two important reactions of the present invention (water electrolysis and nitrogen activation) take place in two separate, isolated reaction chambers, respectively, which ensures that all the energy of the plasma is used directly to activate the nitrogen gas and facilitates the collection of the gas. The method is used as a chemical chain ammonia preparation method, and in the ammonia synthesis process, each step reaction can be carried out under different reactors and reaction conditions, so that the whole reaction system can be optimized one by one to achieve the optimal effect, and N is avoided 2 And H 2 The problem of competing adsorption on the surface of the catalyst,solves the thermodynamic and kinetic contradiction of catalytic synthesis of ammonia, improves the problems that the reaction rate is too slow at low temperature and the excessive temperature is not beneficial to the heat release reaction, ensures higher nitrogen fixation efficiency and relieves NH 3 Decomposition of NH in favor of 3 And (4) collecting. Simultaneously, coupling the plasma technology with the chemical looping technology, N 2 Conversion of molecules to highly active, excited state N 2 Molecules, a gas-solid fluidized reaction zone is formed by utilizing high-speed plasma jet flow, the heat transfer and mass transfer characteristics are enhanced, and N with high reaction activity is formed 2 The plasma is in sufficient contact with the nitrogen carrier and reacts.
The downstream heat of the jet plasma reactor can be used as a heat source of a nitrogen absorption reaction area, the heat required by the nitrogen absorption reaction can be simultaneously provided by the downstream waste heat of the jet plasma reactor and the heating furnace cover 23, and the reasonable temperature is maintained by matching with a temperature controller, so that the investment of the industrial process is reduced, the practical application is facilitated, and the energy utilization rate is improved.
After the nitrogen carrier is subjected to hydrogenation and nitrogen release reaction, the nitrogen carrier reduced to the initial state returns to the nitrogen absorption reaction zone through the return pipe 25 to be nitrified again for circulation, so that the investment in the chemical-looping ammonia production process is reduced, and the waste in the industrial process is reduced.
The above-described embodiments are intended to illustrate rather than to limit the invention, and any modifications and variations of the present invention are within the spirit of the invention and the scope of the appended claims.
Claims (10)
1. An atmospheric-pressure ammonia production device based on plasma activation and chemical chain coupling is characterized by comprising a reactor, a supply system and a power supply;
the reactor comprises a plasma jet reactor, a nitrogen absorption reactor, a nitrogen release reactor and a water electrolysis hydrogen production reactor; the plasma jet reactor comprises a high-voltage electrode and a grounding electrode to form a plasma discharge area, and is connected with the nitrogen absorption reactor and used for activating nitrogen and sending the nitrogen to the nitrogen absorption reactor to react with a nitrogen carrier; the top of the nitrogen absorption reactor is communicated with a cyclone separator through a pipeline, a nitrogen carrier output port of the cyclone separator is connected with the nitrogen release reactor through a pipeline, and a feed back pipeline is also arranged between the lower part of the nitrogen release reactor and the nitrogen absorption reactor and is used for refluxing the nitrogen carrier reduced by the hydrogen; the water electrolysis hydrogen production reactor is connected with the nitrogen release reactor through a single-stage separator;
the supply system is connected with a flow control device and comprises a water vapor supply system and a nitrogen gas supply system, and the water vapor supply system is connected with the electrolytic cell reactor and is used for supplying water vapor for water electrolysis reaction; the nitrogen gas supply system is connected with the plasma jet reactor and is used for supplying nitrogen gas;
the power supply comprises a plasma power supply and a water electrolysis hydrogen production power supply; the plasma power supply is used for supplying power to the high-voltage electrode in the plasma jet reactor;
the water electrolysis hydrogen production power supply takes a new energy power generation mode which cannot be connected to the grid as a source, is used for supplying power for an electrochemical hydrogen evolution reaction in a water electrolysis hydrogen production reactor, and finally completes the preparation of ammonia gas under the normal pressure condition by taking nitrogen storage and discharge of a nitrogen carrier as a core and coupling a plasma technology.
2. The atmospheric-pressure ammonia plant based on plasma activation and chemical looping coupling as recited in claim 1, wherein a temperature monitoring device is connected to the reactor.
3. The atmospheric-pressure ammonia generator based on plasma activation and chemical looping coupling of claim 1, wherein the water vapor supply system comprises a water pump, a water vapor generator and a water vapor inlet valve, the water pump is used for supplying water to the water vapor generator, and the generated water vapor enters the water electrolysis hydrogen production reactor through the water vapor inlet valve and the water vapor inlet valve.
4. The plasma activation and chemical looping coupling based atmospheric pressure ammonia plant of claim 1, wherein the nitrogen gas supply system comprises a nitrogen gas cylinder for storing nitrogen gas, a mass flow controller and a nitrogen gas valve for controlling the flow of nitrogen gas.
5. The atmospheric-pressure ammonia generator based on plasma activation and chemical-looping coupling of claim 1, wherein the pulsating jet plasma reactor comprises an outer electrode, an inner electrode, N 2 The air inlet, the base, the material return pipe, the quartz cover and the air distribution plate are arranged on the base;
the outer electrode is of a hollow columnar structure, is fixed on the base and is connected with the low-voltage end of the plasma power supply; the inner electrode is arranged at the lower position in the hollow structure of the outer electrode and is integrally formed by a lower cylinder and an upper circular table, the bottom of the inner electrode is fixed on the base and is connected with the high-voltage end of the plasma power supply through an electrode lead sheet penetrating through the base; the outer wall of the inner electrode is parallel to the inner wall of the outer electrode;
the wall surface of the outer electrode is provided with two paths of N with the same height 2 Wind inlet, two paths N 2 The air inlet is oppositely flushed to tangentially intake air, so that the introduced N is 2 A spirally rising gas flow is formed in the gap between the inner electrode and the outer electrode.
6. The atmospheric-pressure ammonia plant based on plasma activation and chemical looping coupling of claim 5, wherein the nitrogen-absorbing reactor comprises: the device comprises a material return pipe, a quartz cover and an air distribution plate;
the quartz cover is fixed at the top of the outer electrode and is provided with a temperature control device; the air distribution plate is transversely fixed on the inner wall of the bottom of the quartz cover; the top of the quartz cover is communicated with the cyclone separator through a pipeline, the nitrogen carrier output port of the cyclone separator is connected with the nitrogen release reactor through a pipeline, and the nitrogen carrier reduced to the initial state by hydrogen is communicated with the feed back port of the quartz cover through the feed back pipeline of the nitrogen release reactor.
7. The atmospheric-pressure ammonia production device based on plasma activation and chemical chain coupling as claimed in claim 6, wherein the nitrogen carrier is a metal nitrogen carrier, and is used for matching the temperature of the pulsating jet plasma reactor, the heat at the downstream of the pulsating jet plasma reactor is used as a heat source of a nitrogen absorption reaction zone, and Fe and Mn with nitrides in various valence states are used as the nitrogen carrier, and the nitrogen fixation reaction is carried out at 700 ℃ -900 ℃.
8. The atmospheric-pressure ammonia production device based on plasma activation and chemical chain coupling as claimed in claim 1, wherein the power supply for hydrogen production by water electrolysis is a direct-current power supply device, wherein one end of a negative electrode wire is connected with a hydrogen evolution electrode of the electrolytic cell, and the other end of the negative electrode wire is connected with a negative electrode of the direct-current power supply; one end of the positive wire is connected with the oxygen evolution electrode of the electrolytic cell, and the other end is connected with the positive electrode of the direct current power supply.
9. The atmospheric-pressure ammonia plant based on plasma activation and chemical-looping coupling of claim 1, wherein the water electrolysis hydrogen production reactor is a solid polymer electrolytic cell reaction chamber or a solid oxide electrolytic cell reaction chamber.
10. An atmospheric ammonia production method based on plasma activation and chemical chain coupling, which is carried out by using the device of any one of claims 1 to 9, and is characterized by comprising the following steps:
step 1, installing and connecting a plasma jet and chemical chain coupling ammonia production device;
step 2, opening a nitrogen valve to introduce nitrogen into the plasma jet reactor, and discharging impurity gases in a system and a pipeline; bottom hedging tangential inlet N of plasma jet reactor 2 A spiral ascending air current is formed,
step 3, starting a temperature control device and keeping the temperature at a preset temperature; the downstream heat of the plasma jet reactor and a heating furnace cover are used as nitrogen absorption reaction heat sources, the temperature of a nitrogen absorption reaction chamber is controlled by a temperature controller, and the temperature value is monitored in real time;
step 4, switching on a plasma power supply and a water electrolysis hydrogen production device power supply, connecting an outer electrode and an inner electrode with a pulsating direct current high-voltage power supply, and forming N between the inner electrode and the outer electrode under the driving of high voltage 2 Discharge arcThe discharge arc is driven by the spiral airflow to form a plurality of plasma micro-jet flows through the air distribution plate and then is sprayed into the nitrogen absorption reaction area of the quartz cover to react with the nitrogen carrier;
opening a steam inlet valve to inject steam into the solid polymer electrolytic cell reactor or the solid oxide electrolytic cell reaction chamber through a steam inlet pipe;
the water vapor is electrolyzed in an electrolytic cell to generate hydrogen and oxygen, the oxygen is discharged after passing through a single-stage separator, the hydrogen enters a nitrogen release reactor through a conveying pipe after being pressurized by a centrifugal pump, and the hydrogen generated in the hydrogen enters the nitrogen release reactor through a gas conveying pipeline after passing through the single-stage separator;
the nitrogen carrier which completes the nitrogen absorption reaction in the nitrogen absorption reactor enters a cyclone separator through a pipeline to complete the separation of the nitrogen carrier and nitrogen, the separated nitrogen carrier enters a nitrogen release reactor to be contacted with hydrogen which enters a reaction chamber through a gas pipeline and to generate the hydrogen absorption and nitrogen release reaction to generate ammonia gas, and the nitrogen carrier is reduced to an initial state and then returns to the nitrogen absorption reactor through a material return pipeline to be circulated.
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| CN202211536646.2A CN115818666A (en) | 2022-12-01 | 2022-12-01 | Normal-pressure ammonia production device and method based on plasma activation and chemical chain coupling |
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