CN114540858B - Jet plasma coupling multistage electro-catalysis integrated ammonia synthesis system and method - Google Patents
Jet plasma coupling multistage electro-catalysis integrated ammonia synthesis system and method Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 54
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 47
- 230000008878 coupling Effects 0.000 title claims abstract description 19
- 238000010168 coupling process Methods 0.000 title claims abstract description 19
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 title abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 58
- 238000003860 storage Methods 0.000 claims abstract description 43
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 34
- 230000000694 effects Effects 0.000 claims abstract description 9
- 238000004064 recycling Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 98
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 30
- 230000001105 regulatory effect Effects 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000010453 quartz Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 230000001276 controlling effect Effects 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000005086 pumping Methods 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 238000004891 communication Methods 0.000 claims description 6
- 230000001939 inductive effect Effects 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 230000001360 synchronised effect Effects 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 230000003139 buffering effect Effects 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 238000009616 inductively coupled plasma Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000011943 nanocatalyst Substances 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- 238000007740 vapor deposition Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 2
- 210000002381 plasma Anatomy 0.000 description 82
- 210000004027 cell Anatomy 0.000 description 71
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 238000007036 catalytic synthesis reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/70—Assemblies comprising two or more cells
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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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
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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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/27—Ammonia
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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Abstract
The invention discloses a jet plasma coupling multistage electro-catalysis integrated ammonia synthesis system and a method, which firstly utilize solar energy to drive jet plasma to convert air into NO x And improves water-soluble NO through means such as a gas storage tank and tail gas recycling x The concentration provides reaction raw materials for the electrocatalytic process; then, a plurality of H-shaped electrolytic cells are connected in series to realize multistage catalysis, and meanwhile, the prepared high-catalytic-activity nitrogen-phosphorus-doped molybdenum disulfide electrocatalyst is adopted to furthest improve the conversion efficiency of the electrocatalyst process, and finally, N in the air is obtained 2 Conversion to NH in electrolyte in real time 3 The high-efficiency conversion from renewable solar energy to high-grade chemical energy is realized, and the energy consumption problem in the plasma process is solved.
Description
Technical Field
The invention relates to the field of ammonia synthesis, in particular to a jet plasma coupling multistage electro-catalysis integrated ammonia synthesis system and method.
Background
In the current society, along with the environmental pollution caused by the development of industry and population growth, the development of a green and environment-friendly renewable energy source is a focus of global attention. Ammonia gas is used as an excellent storage carrier of hydrogen energy and is also used as an important nitrogenous fertilizer raw material for agricultural production, so that the method has wide application in the fields of agriculture and energy storage, and how to efficiently prepare clean and environment-friendly ammonia gas becomes a significant subject in the fields of energy and environment. Currently, the ammonia production method applied industrially is a Habai method developed in the last century, and the method continuously provides the required ammonia resource for the human society for more than one hundred years, however, the method has the advantages of harsh reaction conditions, high energy consumption and emission of nearly 3 hundred million tons of carbon dioxide in the year; the large amount of high-nitrogen ammonia wastewater generated in the production process causes great pollution to the environment. Therefore, at the present moment that the energy and environment problems are increasingly prominent, the development of a clean and efficient ammonia production means capable of replacing the Habai method is urgent.
At present, many experimental researches directly convert nitrogen into ammonia through an electrocatalytic method, the experimental conditions are mild, the method is concise and environment-friendly, and no harmful pollutant is discharged. However, since the electrocatalytic method is excessively dependent on the performance of the catalyst, the nitrogen-nitrogen triple bond (N≡N,948 kJ/mol) with stable structure cannot be effectively broken, so that the problems of poor treatment capacity and low yield exist, and the requirement of human beings on ammonia cannot be met; based on the method, the invention couples the plasmas with strong processing capability with the electrocatalysis, takes air with rich sources as raw materials, and can also realize N 2 To NH 3 Is transformed by the above method. The strong treatment capacity of the plasmas is utilized, so that the effective breaking of the nitrogen-nitrogen triple bond is ensured, the efficient pollution-free ammonia synthesis can be realized, meanwhile, the plasmas can be well combined with renewable energy sources such as solar energy, wind energy and the like, and an experimental foundation can be provided for replacing a Habai method in the future.
Disclosure of Invention
The invention aims to further optimize and perfect an experimental system of plasma and electrocatalytic coupling, integrate a solar-driven plasma discharging and electrocatalytic process and a corresponding tail gas recycling system into an integrated collectionA system for realizing N from air 2 Into the electrolyte NH 3 And realizing multistage catalysis through serial connection of a plurality of H-shaped electrolytic cells, preparing the nitrogen-phosphorus doped molybdenum disulfide electrocatalyst with high catalytic activity, and finally realizing plasma coupling multistage nitrogen-phosphorus doped molybdenum disulfide electrocatalyst integrated high-efficiency ammonia synthesis.
The aim of the invention is realized by the following technical scheme: the integrated ammonia synthesis system comprises a multi-air inlet jet plasma reactor, a multi-stage electrocatalyst system based on nitrogen-phosphorus doped molybdenum disulfide electrocatalyst and an exhaust gas recirculation system;
the multi-air-inlet jet flow plasma reactor comprises two air inlets, wherein one air inlet is an air inlet and is connected with an air compressor, and the other air inlet is a gas circulation air inlet and is connected with a circulation air pump for gas circulation; the multi-air inlet jet flow plasma reactor is used for leading N in air 2 And O 2 Conversion to NO x The reactor outlet was connected to the gas line via stainless steel flange and quartz cover and was purged with NO x Inputting into a gas storage tank;
the multi-stage electrocatalysis system comprises an electrochemical workstation and an H-type electrolytic cell; a plurality of H-shaped electrolytic cells are connected in series, an air outlet of a cathode reaction chamber of the upper-stage H-shaped electrolytic cell is connected with an air inlet of a cathode reaction chamber of the lower-stage H-shaped electrolytic cell, and each H-shaped electrolytic cell is connected with an electrochemical workstation to realize NO x To NH 3 Is transformed by (a); the first-stage H-shaped electrolytic cell is connected with the gas storage tank; the H-shaped electrolytic cell of the last stage is connected with a circulating air pump;
the working electrode of the H-type electrolytic cell adopts a nitrogen-phosphorus doped molybdenum disulfide electrocatalyst, and the preparation process of the nitrogen-phosphorus doped molybdenum disulfide electrocatalyst comprises the following steps: firstly, sequentially carrying out plasma enhanced vapor deposition and a hydrothermal method, and a phosphating method to obtain phosphorus doped molybdenum disulfide, and finally carrying out ammonia plasma doping on the phosphorus doped molybdenum disulfide to obtain a nitrogen-phosphorus doped molybdenum disulfide electrocatalyst, wherein the plasma doping process is as follows:
placing the phosphated molybdenum disulfide catalyst in a tube furnace, pumping to negative pressure, heating, introducing ammonia gas, discharging by inductive coupling plasma, wherein in the discharging process, the etching effect on the surface of the catalyst is obvious due to the ammonia gas atmosphere, and the generated N-containing free radical has high activity and can replace S atoms in molybdenum disulfide to realize N atom doping, so that the nitrogen-phosphorus doped molybdenum disulfide electrocatalyst is obtained;
the tail gas recirculation system comprises a first mass flowmeter, a pressure gauge, a pressure regulating valve, a gas storage tank, a ventilation valve, a second mass flowmeter and a circulating air pump; the first mass flowmeter is arranged at an air inlet of the reactor and used for controlling the inlet air flow; the plasma discharge gas is regulated by a second mass flowmeter and a pressure regulating valve and then is introduced into a gas storage tank, and then flows through each level of H-type electrolytic cells and flows back to the multi-gas inlet jet plasma reactor through a circulating gas pump; the tail gas recycling system contains N which does not participate in the reaction 2 、O 2 NO based NO x The tail gas of the gas is participated in discharge again, and the gas after being treated again by the plasma is easier to be converted into water-soluble NO x The gas conversion rate is improved.
Further, the system also comprises a solar power supply system, wherein the solar power supply system comprises a solar panel, a storage battery and a transformer; the solar panel is connected with a storage battery, and the storage battery supplies power to the multi-air inlet jet flow plasma reactor through a transformer.
Further, the air inlets of the multi-air inlet jet flow plasma reactor are a plurality of tangential air inlets which are uniformly distributed, a rotary air flow is formed in the reactor, disturbance of the air in the air cavity of the reactor is increased, discharge effect and plasma area are enhanced, and gas treatment efficiency is improved.
Further, since the discharge gas contains a large amount of NO, the gas is easily oxidized to NO in an oxygen-containing environment 2 Through standing the gas storage tank and buffering the discharge gas, the water-soluble NO in the discharge gas x Increased content, more NO x Fixed in solution.
Further, the preparation method of the nitrogen-phosphorus doped molybdenum disulfide electrocatalyst comprises the following steps:
(1) Cutting carbon with proper size, arranging the carbon in a quartz tube, pumping the carbon to negative pressure, then introducing methane, hydrogen and argon into the quartz tube according to a certain proportion, heating, starting cooling water, discharging for a period of time through inductively coupled plasma, and forming uniformly distributed graphene on carbon cloth, and recording as VG/CC;
(2) Uniformly mixing 1.2g of sodium molybdate, 1.56g of thioacetamide and 60ml of deionized water, then transferring into a reaction kettle, placing the obtained VG/CC into a mixed solution, and carrying out hydrothermal treatment in an oven at 200 ℃ for 12 hours to obtain a molybdenum disulfide nano structure growing on vertical graphene, and recording as MoS 2 /VG/CC；
(3) The prepared MoS 2 Respectively placing/VG/CC and 1g sodium hypophosphite at two ends of quartz boat, placing into quartz tube, wherein MoS 2 VG/CC is positioned in the downwind direction, sodium hypophosphite is positioned in the upwind direction, the negative pressure is pumped, the reaction is maintained for one hour at 300 ℃, and the phosphorus doped molybdenum disulfide catalyst is obtained after the reaction is finished;
(4) Placing a phosphorus-doped molybdenum disulfide catalyst in a tube furnace, pumping to negative pressure, introducing ammonia gas, heating, and performing inductive coupling plasma discharge to obtain a nitrogen-phosphorus-doped molybdenum disulfide nano catalyst, which is denoted as N, P-MoS 2 /VG/CC。
The invention also provides a jet plasma coupling multistage electro-catalysis integrated ammonia synthesis method, which is a multistage catalysis operation mode in which gas discharge and an electro-catalysis process are synchronously carried out, and comprises the following steps:
(1) Connecting the multi-air-inlet jet plasma reactor with a power supply, respectively connecting two air inlets with an air compressor and a circulating air pump, starting the air compressor, introducing air into the multi-air-inlet jet plasma reactor, and controlling the air inlet flow by a first mass flowmeter;
(2) The power of the plasma power supply is turned on, the power input to the two ends of the multi-air inlet jet flow plasma reactor is regulated, the stable discharge of the plasma is realized, and N in the air is removed 2 And O 2 Conversion to NO x Is input into a gas storage tankIn (a) and (b);
(3) The gas outlet of the gas storage tank is connected with the gas inlet of the first-stage H-shaped electrolytic cell, the gas outlet of the upper-stage H-shaped electrolytic cell is connected with the lower-stage H-shaped electrolytic cell through a gas pipe, and the last-stage H-shaped electrolytic cell is connected with a circulating gas pump; each electrolytic cell is respectively connected with an electrochemical workstation, and a piece of nitrogen-phosphorus doped molybdenum disulfide electrocatalyst is clamped on a working electrode clamp of each H-shaped electrolytic cell to serve as a working electrode.
(4) Regulating a pressure regulating valve and a communication valve to keep the pressure of pipeline gas stable, starting an electrochemical workstation, operating a CV to stabilize the current of a system, and then performing all levels of electrocatalytic processes, wherein the processes comprise first level electrocatalytic, second level electrocatalytic and third level electrocatalytic … Nth level electrocatalytic, simultaneously starting a magnetic stirrer, uniformly mixing electrolyte through a magnetic stirrer, realizing synchronous implementation of plasma discharge and electrocatalytic, and collecting reaction liquid in each H-type electrolytic cell for ammonia yield detection after the reaction is finished.
Further, the electrocatalytic reaction was carried out at an overpotential of 0.1V to 0.5V for 1 hour, and the ammonia yield was detected by an ultraviolet-spectrophotometer.
The invention has the beneficial effects that:
(1) Integrating the system; through integrated design, including the connection of plasma reactor and electrolytic cell, the construction of tail gas recovery system etc. integrates the solar-driven plasma discharge and electrocatalytic processes into an integrated system, thereby achieving the synchronous operation of the plasma discharge and electrocatalytic processes and realizing N in the air 2 Into the electrolyte NH 3 Is converted in real time.
(2) The conversion efficiency is high; conversion efficiency includes both air to water-soluble NO x And includes the conversion efficiency of NO in solution 2 - ,NO 3 - To NH 3 Is not limited, and the conversion efficiency of the catalyst is improved. The former improves the air to water-soluble NO through the strong treatment capability of multi-air inlet jet flow plasmas, the standing function of an air storage tank and the tail gas recycling of a tail gas recycling system x Provides sufficient raw materials for the subsequent electrocatalytic process; rear part (S)The nitrogen-phosphorus doped molybdenum disulfide catalyst with high catalytic activity is used as a working electrode for electrocatalytic reaction, so that the reaction rate of synthesizing ammonia in the electrolyte is improved; meanwhile, the multistage catalytic system established by a plurality of H-shaped electrolytic cells in series improves NO in the electrocatalytic process to the greatest extent 2 - ,NO 3 - Conversion to NH 3 Is finally combined to improve N 2 To NH 3 Is not limited, and the conversion efficiency of the catalyst is improved.
(3) Low energy consumption and no pollution; the clean renewable solar energy is used as the power supply energy of the plasma reactor, so that the huge energy consumption required by plasma discharge is effectively eliminated; meanwhile, a plasma coupling electrocatalytic method is adopted to realize the carbon neutralization in the reaction process; in addition, NO in the tail gas x The recycling can achieve zero pollution and zero emission in the whole process.
(4) The reaction design is reasonable; the experimental system effectively solves the problems that the triple bond of nitrogen and nitrogen is difficult to break and the reaction activity of synthetic ammonia is low in the current research, utilizes plasma to reform the broken bond of nitrogen and oxygen in the air, avoids directly taking the nitrogen into reaction, and dissolves the reformed nitrogen-oxygen compound in electrolyte for electrocatalytic reaction, thereby greatly improving the reaction rate of the synthetic ammonia.
Drawings
FIG. 1 is a schematic diagram of a jet plasma coupled multi-stage electrocatalytic integrated ammonia synthesis system.
In the figure: 1. a solar panel; 2. a storage battery; 3. a transformer; 4. an air compressor; 5. a first mass flow meter; 6. a multi-inlet jet plasma reactor; 7. stainless steel flanges; 8. a quartz cover; 9. a pressure gauge; 10. a pressure regulating valve; 11. a gas storage tank; 12. a vent valve; 13. a second mass flow meter; 14. an electrochemical workstation; 15. a magnetic stirrer; an h-type electrolytic cell; 17. a magnetic stirrer; 18. nitrogen-phosphorus doped molybdenum disulfide electrocatalyst; 19. second stage electrocatalysis; 20. third stage electrocatalysis; 21. stage N electrocatalysis; 22. and a circulating air pump.
Fig. 2 is a graph comparing experimental performance: (a) Single-stage catalytic synthesis of ammonia at different overpotential yields and corresponding faraday efficiencies; (b) Multistage catalytic synthesis of ammonia at different overpotential yields and corresponding faraday efficiencies; (c) Multistage catalytic synthesis of ammonia with different catalysts under 0.3V overpotential is performed, and the corresponding Faraday efficiency is achieved;
FIG. 3 is a diagram of a nitrogen-phosphorus doped molybdenum disulfide (a) scanning electron microscope and (b) transmission electron microscope.
FIG. 4 is a graph of X-ray photoelectron spectrum of nitrogen-phosphorus doped molybdenum disulfide (upper: N, P-MoS) 2 VG/CC; the following steps: moS (MoS) 2 /VG/CC)。
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to the drawings.
The invention provides a jet plasma coupling multistage electro-catalysis integrated ammonia synthesis system and a method. Firstly, solar energy is utilized to drive jet flow plasma to convert air into NO x And improves water-soluble NO through means such as a gas storage tank and tail gas recycling x The concentration provides reaction raw materials for the electrocatalytic process; then, a plurality of H-shaped electrolytic cells are connected in series to realize multistage catalysis, and meanwhile, the prepared high-catalytic-activity nitrogen-phosphorus-doped molybdenum disulfide electrocatalyst is adopted to furthest improve the conversion efficiency of the electrocatalyst process, and finally, N in the air is obtained 2 Conversion to NH in electrolyte in real time 3 The high-efficiency conversion from renewable solar energy to high-grade chemical energy is realized, and the energy consumption problem in the plasma process is solved.
As shown in fig. 1, the integrated ammonia synthesis system with jet plasma coupled with multi-stage electrocatalysis comprises a solar power supply system, a multi-air inlet jet plasma reactor 6, a multi-stage electrocatalysis system based on nitrogen-phosphorus doped molybdenum disulfide electrocatalyst and an exhaust gas recirculation system;
the multi-air inlet jet flow plasma reactor 6 comprises two air inlets, wherein one air inlet is an air inlet and is connected with the air compressor 4, and the other air inlet is a gas circulation air inlet and is connected with the circulation air pump 22 for gas circulation; the air inlet of the multi-air inlet jet flow plasma reactor 6 is provided with a plurality of evenly distributed cutsAnd a rotary airflow is formed in the reactor towards the air inlet, so that the disturbance of the gas in the air cavity of the reactor and the discharge area of plasma are increased, the discharge effect is enhanced, and the gas treatment efficiency is improved. The multi-air inlet jet flow plasma reactor 6 is used for mixing N in air 2 And O 2 Conversion to NO x Is input into the air storage tank 11; by the air storage tank 11 standing and buffering the discharge gas, the water-soluble NO in the discharge gas x Increased content of NO x Is fixed in the solution to provide the reaction raw material for the electrocatalytic process.
The multi-stage electrocatalysis system comprises an electrochemical workstation 14 and an H-cell 16; a plurality of H-shaped electrolytic cells 16 are connected in series, an air outlet of a cathode reaction chamber of the upper H-shaped electrolytic cell 16 is connected with an air inlet of a cathode reaction chamber of the lower H-shaped electrolytic cell 16, and each H-shaped electrolytic cell 16 is connected with an electrochemical workstation 14 to realize NO x To NH 3 Is transformed by (a); the first-stage H-shaped electrolytic cell 16 is connected with the gas storage tank 11; the H-shaped electrolytic cell 16 of the last stage is connected with a circulating air pump 22;
unlike other reactions, a large amount of NO is generated in the plasma process of the coupling system x The single-stage electrocatalytic process cannot be effectively converted and utilized, and NO is maximally utilized by establishing a multi-stage catalytic system x Multistage absorption in electrolyte and greatly improves NH 3 Is improved.
The working electrode of the H-type electrolytic cell 16 adopts a nitrogen-phosphorus doped molybdenum disulfide electrocatalyst 18, and the preparation process of the nitrogen-phosphorus doped molybdenum disulfide electrocatalyst 18 comprises the following steps: firstly, sequentially carrying out plasma enhanced vapor deposition and a hydrothermal method, and a phosphating method to obtain phosphorus doped molybdenum disulfide, and finally carrying out ammonia plasma doping on the phosphorus doped molybdenum disulfide to obtain a nitrogen-phosphorus doped molybdenum disulfide electrocatalyst, wherein the plasma doping process is as follows:
placing the phosphated molybdenum disulfide catalyst in a tube furnace, pumping to negative pressure, heating, introducing ammonia gas, and discharging by inductive coupling plasma, wherein generated N-containing free radicals replace S atoms in molybdenum disulfide to realize N-atom doping, so as to obtain a nitrogen-phosphorus doped molybdenum disulfide electrocatalyst 18;
the preparation method of the nitrogen-phosphorus doped molybdenum disulfide electrocatalyst 18 specifically comprises the following steps:
(1) Cutting carbon with proper size, arranging the carbon in a quartz tube, pumping the carbon to negative pressure, then introducing methane, hydrogen and argon into the quartz tube according to a certain proportion, heating, starting cooling water, discharging for a period of time through inductively coupled plasma, and forming uniformly distributed graphene on carbon cloth, and recording as VG/CC;
(2) Uniformly mixing 1.2g of sodium molybdate, 1.56g of thioacetamide and 60ml of deionized water, then transferring into a reaction kettle, placing the obtained VG/CC into a mixed solution, and carrying out hydrothermal treatment in an oven at 200 ℃ for 12 hours to obtain a molybdenum disulfide nano structure growing on vertical graphene, and recording as MoS 2 /VG/CC；
(3) The prepared MoS 2 Respectively placing/VG/CC and 1g sodium hypophosphite at two ends of quartz boat, placing into quartz tube, wherein MoS 2 VG/CC is positioned in the downwind direction, sodium hypophosphite is positioned in the upwind direction, the negative pressure is pumped, the reaction is maintained for one hour at 300 ℃, and the phosphorus doped molybdenum disulfide catalyst is obtained after the reaction is finished;
(4) Placing a phosphorus-doped molybdenum disulfide catalyst in a tube furnace, pumping to negative pressure, introducing ammonia gas, heating, and performing inductive coupling plasma discharge to obtain a nitrogen-phosphorus-doped molybdenum disulfide nano catalyst, which is denoted as N, P-MoS 2 /VG/CC。
The tail gas recirculation system comprises a first mass flowmeter 5, a pressure regulating valve 10, a gas storage tank 11, a second mass flowmeter 13 and a circulating air pump 22; the first mass flowmeter 5 is arranged at an air inlet of the reactor and is used for controlling the inlet air flow; the plasma discharge gas is regulated by a second mass flowmeter 13 and a pressure regulating valve 10 and then is introduced into a gas storage tank 11, and then flows through each stage of H-type electrolytic cells 16 and then flows back to the multi-gas inlet jet flow plasma reactor 6 through a circulating air pump 22; the tail gas recycling system contains N which does not participate in the reaction 2 、O 2 NO based NO x The tail gas of the gas is participated in discharge again, and the gas after being treated again by the plasma is easier to be converted into water-soluble NO x Improves the gas conversion rate. Through the recovery of tail gas, not only the gas conversion rate is improved, but also harmful NO is avoided x And (3) discharging the gas.
The solar power supply system comprises a solar panel 1, a storage battery 2 and a transformer 3; the solar panel 1 is connected with the storage battery 2, and the storage battery 2 supplies power to the multi-air inlet jet plasma reactor 6 through the transformer 3.
The invention also provides a jet plasma coupling multistage electro-catalysis integrated ammonia synthesis method, which is a multistage catalysis operation mode in which gas discharge and an electro-catalysis process are synchronously carried out, and comprises the following steps:
(1) Connecting the multi-air inlet jet flow plasma reactor 6 with a power supply, respectively connecting two air inlets with an air compressor 4 and a circulating air pump 22, starting the air compressor 4, introducing air into the multi-air inlet jet flow plasma reactor 6, and controlling the air inlet flow by a first mass flowmeter 5;
(2) The power of the plasma power is turned on, the power input to the two ends of the multi-air inlet jet flow plasma reactor 6 is regulated, the stable discharge of the plasma is realized, and N in the air is removed 2 And O 2 Conversion to NO x Is input into the air storage tank 11;
(3) The air outlet of the air storage tank 11 is connected with the air inlet of the first-stage H-shaped electrolytic cell 16, the air outlet of the upper-stage H-shaped electrolytic cell 16 is connected with the lower-stage H-shaped electrolytic cell 16 through an air pipe, and the last-stage H-shaped electrolytic cell 16 is connected with the circulating air pump 22; each of which has an electrochemical workstation 14 attached thereto and a piece of nitrogen and phosphorus doped molybdenum disulfide electrocatalyst 18 as a working electrode is held on a working electrode clamp of each H-type cell 16.
(4) The pressure regulating valve 10 and the communication valve 12 are regulated to maintain the pressure of pipeline gas stable, the electrochemical workstation 14 is started, the system current is stabilized by running CV, then a multistage electro-catalysis process is carried out, the synchronous carrying out of plasma discharge and electro-catalysis is realized, the electro-catalysis reaction is carried out for 1 hour under the overpotential of 0.1V-0.5V, after the reaction is finished, the reaction liquid in each H-type electrolytic cell is collected, and the ammonia yield is detected by an ultraviolet-spectrophotometer.
Examples 1 to 5
As shown in (a) of fig. 2, the jet plasma reactor is connected with a power supply, three air inlets are respectively connected with an air compressor and a circulating air pump, the outlet end of the reactor is fixed with a quartz cover through a flange, the air outlet of the quartz cover is connected with the air inlet of an air storage tank through an air pipe, the air outlet of the air storage tank is connected with the air inlet of an H-shaped electrolytic cell, and the pressure of pipeline gas is regulated by a pressure regulating valve and a communication valve, so that the gas flow is kept stable;
clamping a prepared nitrogen-phosphorus doped molybdenum disulfide electrocatalyst on a working electrode clamp of an H-type electrolytic cell to serve as a working electrode, respectively filling a certain amount of 0.1M KOH solution into the H-type electrolytic cell as shown in a microstructure shown in figure 3, placing the H-type electrolytic cell on a magnetic stirrer, continuously stirring the H-type electrolytic cell by using a magnetic stirrer, connecting an electrochemical workstation with the H-type electrolytic cell, starting an air compressor, and controlling air inflow through a mass flowmeter; and (3) turning on a plasma power supply, adjusting the power input into two ends of the three-inlet jet flow plasma reactor to realize stable discharge of plasma, simultaneously turning on an electrochemical workstation, operating CV to stabilize the current of the system, performing a single-stage electro-catalysis process for 1 hour under the overpotential of 0.1V/0.2V/0.3V/0.4V/0.5V, and collecting the reaction solution in the H-type electrolytic cell to detect the ammonia yield after the reaction is finished.
Examples 6 to 10
As shown in (b) of fig. 2, the jet plasma reactor is connected with a power supply, three air inlets are respectively connected with an air compressor and a circulating air pump, the outlet end of the reactor is fixed with a quartz cover through a flange, the air outlet of the quartz cover is connected with the air inlet of an air storage tank through an air pipe, the air outlet of the air storage tank is connected with the air inlet of a first-stage H-shaped electrolytic cell, the air outlet of a previous-stage electrolytic cell is connected with a next-stage electrolytic cell through the air pipe, and the pressure of pipeline gas is regulated by a pressure regulating valve and a communication valve, so that the flow of the gas is kept stable;
respectively clamping a prepared nitrogen-phosphorus doped molybdenum disulfide electrocatalyst on working electrode clamps of two H-type electrolytic cells as working electrodes, respectively filling a certain amount of 0.1M KOH solution into the two H-type electrolytic cells as shown in a graph in fig. 3, placing the two H-type electrolytic cells on a magnetic stirrer, continuously stirring the two H-type electrolytic cells by using a magnetic stirrer, respectively connecting the two electrochemical working stations with the corresponding H-type electrolytic cells, starting an air compressor, and controlling the gas flow through a mass flowmeter; and (3) turning on a plasma power supply, adjusting the power input into two ends of the three-inlet jet flow plasma reactor to realize stable discharge of plasma, simultaneously turning on an electrochemical workstation, running CV to stabilize the current of the system, and then performing a two-stage electrocatalytic process for 1 hour under the overpotential of 0.1V/0.2V/0.3V/0.4V/0.5V, and collecting the reaction liquid in each H-type electrolytic cell to detect the ammonia yield after the reaction is finished.
Examples 11 to 14
As shown in (c) of fig. 2, the jet plasma reactor is connected with a power supply, three air inlets are respectively connected with an air compressor and a circulating air pump, the outlet end of the reactor is fixed with a quartz cover through a flange, the air outlet of the quartz cover is connected with the air inlet of an air storage tank through an air pipe, the air outlet of the air storage tank is connected with the air inlet of a first-stage H-shaped electrolytic cell, the air outlet of a previous-stage electrolytic cell is connected with a next-stage electrolytic cell through the air pipe, and the pressure of pipeline gas is regulated by a pressure regulating valve and a communication valve, so that the flow of the gas is kept stable;
clamping CC, VG/CC and MoS on working electrode clamps of two H-shaped electrolytic cells 2 /VG/CC、N,P-MoS 2 VG/CC as working electrode, moS 2 VG/CC and N, P-MoS 2 The X-ray photoelectron spectrum of the VG/CC is shown as figure 4, a certain amount of 0.1M KOH solution is respectively filled into two H-type electrolytic cells, the two H-type electrolytic cells are placed on a magnetic stirrer and continuously stirred by a magnetic stirrer, two electrochemical workstations are respectively connected with the corresponding H-type electrolytic cells, an air compressor is started, and the gas flow is controlled by a mass flowmeter; the method comprises the steps of turning on a plasma power supply, adjusting power input into two ends of a three-inlet jet flow plasma reactor to realize stable discharge of plasma, simultaneously turning on an electrochemical workstation, performing a two-stage electrocatalytic process for 1 hour under an overpotential of 0.3V after running CV to stabilize system current, and collecting each H-type electricity after the reaction is finishedThe reaction solution in the solution tank was subjected to detection of ammonia yield.
Example 15
The jet flow plasma reactor is connected with a power supply, three air inlets are respectively connected with an air compressor and a circulating air pump, the outlet end of the reactor is fixed with a quartz cover through a flange, the air outlet of the quartz cover is connected with the air inlet of an air storage tank through an air pipe, the air outlet of the air storage tank is connected with the air inlet of a first-stage H-shaped electrolytic cell, the air outlet of a previous-stage electrolytic cell is connected with a next-stage electrolytic cell through the air pipe, and the air pressure of an air circuit system is regulated by a pressure valve, so that the air flow is kept stable;
respectively filling a certain amount of 0.1M KOH solution into two H-shaped electrolytic cells, placing the two H-shaped electrolytic cells on a magnetic stirrer, continuously stirring the two H-shaped electrolytic cells by using a magnetic stirrer, starting a gas cylinder, introducing air, and controlling the gas flow by using a mass flowmeter; and (3) turning on a plasma power supply, adjusting the power input into two ends of the three-air-inlet jet flow plasma reactor, realizing stable discharge of plasma, and collecting reaction liquid in two H-type electrolytic cells after 1 hour to detect the ammonia yield.
Example 16
The prepared nitrogen-phosphorus doped molybdenum disulfide electrocatalyst is used as a working electrode to be clamped on working electrode clamps of two electrolytic cells, the microcosmic appearance is shown in figure 3, a certain amount of 0.1M KOH solution is respectively filled into the two H-type electrolytic cells, the two H-type electrolytic cells are placed on a magnetic stirrer and are continuously stirred by a magnetic stirrer, two electrochemical workstations are respectively connected with the corresponding H-type electrolytic cells, a gas cylinder is opened, air is directly introduced into the electrolytic cells, and the gas flow is controlled by a mass flowmeter; starting an electrochemical workstation, operating CV to stabilize the current of the system, performing a two-stage electrocatalytic process for 1 hour under the overpotential of 0.1V-0.5V, and collecting the reaction liquid in two H-type electrolytic cells after the reaction is finished to detect the ammonia yield.
The method further optimizes and perfects an experimental system of plasma and electrocatalytic coupling: the addition of multiple stages and the application of the nitrogen-phosphorus doped molybdenum disulfide electrocatalyst further improve the ammonia yield. Experiments have shown that at 0.5v overpotential, the ammonia conversion efficiency of two-stage catalysis (7294.06 μg/h) is 1.6 times that of single-stage catalysis (4596.36 μg/h), and all lead the current research level. The invention can be optimized and perfected continuously in future, and is expected to achieve better effect.
The above-described embodiments are intended to illustrate the present invention, not to limit it, and any modifications and variations made thereto are within the spirit of the invention and the scope of the appended claims.
Claims (7)
1. The integrated ammonia synthesis system is characterized by comprising a multi-air inlet jet plasma reactor (6), a multi-stage electrocatalytic system based on a nitrogen-phosphorus doped molybdenum disulfide electrocatalyst and an exhaust gas recirculation system;
the multi-air-inlet jet flow plasma reactor (6) comprises two air inlets, wherein one air inlet is an air inlet and is connected with the air compressor (4), and the other air inlet is a gas circulation air inlet and is connected with the circulation air pump (22) for gas circulation; the multi-air inlet jet flow plasma reactor (6) is used for leading N in the air 2 And O 2 Conversion to NO x Is input into a gas storage tank (11);
the multi-stage electrocatalysis system comprises an electrochemical workstation (14) and an H-cell (16); a plurality of H-shaped electrolytic cells (16) are effectively and serially matched, the air outlet of the cathode reaction chamber of the upper-stage H-shaped electrolytic cell (16) is connected with the air inlet of the cathode reaction chamber of the lower-stage H-shaped electrolytic cell (16), and each H-shaped electrolytic cell (16) is connected with an electrochemical workstation (14) to realize NO x To NH 3 Is transformed by (a); the first-stage H-shaped electrolytic cell (16) is connected with the gas storage tank (11); the last stage H-shaped electrolytic cell (16) is connected with a circulating air pump (22);
the working electrode of the H-type electrolytic cell (16) adopts a nitrogen-phosphorus doped molybdenum disulfide electrocatalyst (18), and the preparation process of the nitrogen-phosphorus doped molybdenum disulfide electrocatalyst (18) is as follows: firstly, uniformly distributed graphene is formed on carbon cloth through plasma enhanced vapor deposition, a molybdenum disulfide nanostructure growing on vertical graphene is obtained through a hydrothermal method, phosphorus doped molybdenum disulfide is obtained through a phosphating method, and finally, ammonia plasma doping is carried out on the phosphorus doped molybdenum disulfide to obtain a nitrogen-phosphorus doped molybdenum disulfide electrocatalyst, wherein the plasma doping process is as follows:
placing the phosphated molybdenum disulfide catalyst in a tube furnace, pumping to negative pressure, heating, introducing ammonia gas, and discharging by inductive coupling plasma, wherein generated N-containing free radicals replace S atoms in molybdenum disulfide to realize N-atom doping, so as to obtain a nitrogen-phosphorus doped molybdenum disulfide electrocatalyst (18);
the tail gas recirculation system comprises a first mass flowmeter (5), a pressure regulating valve (10), a gas storage tank (11), a second mass flowmeter (13) and a circulating air pump (22); the first mass flowmeter (5) is arranged at an air inlet of the reactor and used for controlling the inlet air flow; the plasma discharge gas is regulated by a second mass flowmeter (13) and a pressure regulating valve (10) and then is introduced into a gas storage tank (11), and then flows through each level of H-shaped electrolytic cells (16) and then flows back to the multi-gas inlet jet plasma reactor (6) through a circulating air pump (22); the tail gas recycling system contains N which does not participate in the reaction 2 、O 2 NO based NO x The tail gas of the gas is participated in discharge again, and the gas after being treated again by the plasma is easier to be converted into water-soluble NO x The gas conversion rate is improved.
2. The integrated ammonia synthesis system of jet plasma coupled multistage electrocatalysis according to claim 1, further comprising a solar power supply system comprising a solar panel (1), a battery (2) and a transformer (3); the solar panel (1) is connected with the storage battery (2), and the storage battery (2) supplies power to the multi-air inlet jet flow plasma reactor (6) through the transformer (3).
3. The integrated ammonia synthesis system of jet plasma coupling multistage electrocatalysis according to claim 1, wherein the air inlet of the multi-air inlet jet plasma reactor (6) is a plurality of tangential air inlets which are uniformly distributed, a rotating air flow is formed in the reactor, disturbance of gas in the reactor air cavity and plasma discharge area are increased, discharge effect is enhanced, and gas treatment efficiency is improved.
4. The integrated ammonia synthesis system of jet plasma coupled multistage electrocatalysis according to claim 1, wherein the water-soluble NO in the discharge gas is made by the gas storage tank (11) standing and buffering the discharge gas x Increased content of NO x Fixed in solution.
5. The integrated ammonia synthesis system of jet plasma coupled multi-stage electrocatalyst according to claim 1, wherein the method for preparing the nitrogen-phosphorus doped molybdenum disulfide electrocatalyst (18) comprises the steps of:
(1) Cutting carbon with proper size, arranging the carbon in a quartz tube, pumping the carbon to negative pressure, then introducing methane, hydrogen and argon into the quartz tube according to a certain proportion, heating, starting cooling water, discharging for a period of time through inductively coupled plasma, and forming uniformly distributed graphene on carbon cloth, and recording as VG/CC;
(2) Uniformly mixing 1.2g of sodium molybdate, 1.56g of thioacetamide and 60ml of deionized water, then transferring into a reaction kettle, placing the obtained VG/CC into the mixed solution, and carrying out hydrothermal treatment in an oven at 200 ℃ for 12 hours to obtain a molybdenum disulfide nano structure growing on vertical graphene, which is denoted as MoS 2 /VG/CC；
(3) The prepared MoS 2 Respectively placing/VG/CC and 1g sodium hypophosphite at two ends of quartz boat, placing into quartz tube, wherein MoS 2 VG/CC is positioned in the downwind direction, sodium hypophosphite is positioned in the upwind direction, the negative pressure is pumped, the reaction is maintained for one hour at 300 ℃, and the phosphorus doped molybdenum disulfide catalyst is obtained after the reaction is finished;
(4) Placing a phosphorus-doped molybdenum disulfide catalyst in a tube furnace, pumping to negative pressure, heating, introducing ammonia gas, and performing inductive coupling plasma discharge to obtain a nitrogen-phosphorus-doped molybdenum disulfide nano catalyst, which is denoted as N, P-MoS 2 /VG/CC。
6. A jet plasma coupled multi-stage electrocatalytic integrated ammonia synthesis method based on a system as claimed in any one of claims 1-5, characterized in that it is a multi-stage catalytic operation mode in which the gas discharge and electrocatalytic processes are synchronized, comprising the steps of:
(1) Connecting a multi-air-inlet jet plasma reactor (6) with a power supply, respectively connecting two air inlets with an air compressor (4) and a circulating air pump (22), starting the air compressor (4), introducing air into the multi-air-inlet jet plasma reactor (6), and controlling the air inlet flow by a first mass flowmeter (5);
(2) The power of the plasma power is turned on, the power input to the two ends of the multi-air inlet jet flow plasma reactor (6) is regulated, the stable discharge of the plasma is realized, and N in the air is removed 2 And O 2 Conversion to NO x Is input into a gas storage tank (11);
(3) The air outlet of the air storage tank (11) is connected with the air inlet of the first-stage H-shaped electrolytic cell (16), the air outlet of the upper-stage H-shaped electrolytic cell (16) is connected with the next-stage H-shaped electrolytic cell (16) through an air pipe, and the last-stage H-shaped electrolytic cell (16) is connected with a circulating air pump (22); wherein each electrolytic cell is respectively connected with an electrochemical workstation (14), and a piece of nitrogen-phosphorus doped molybdenum disulfide electrocatalyst (18) is clamped on a working electrode clamp of each H-shaped electrolytic cell (16) to serve as a working electrode;
(4) And regulating the pressure regulating valve (10) and the communication valve (12) to maintain the pressure of pipeline gas stable, starting the electrochemical workstation (14), operating the CV to stabilize the system current, and then performing all levels of electrocatalytic processes to realize synchronous performance of plasma discharge and electrocatalytic, and collecting the reaction liquid in each H-type electrolytic cell to detect the ammonia yield after the reaction is finished.
7. The integrated jet plasma coupled multi-stage electrocatalytic ammonia process as claimed in claim 6, wherein the electrocatalytic reaction is carried out at an overpotential of 0.1V-0.5V for 1 hour, the ammonia yield being detected by uv-spectrophotometer.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109326784A (en) * | 2018-10-19 | 2019-02-12 | 郑州大学 | Phosphorus doping MoS2Load the preparation method and application of graphene nanometer sheet |
| CN110983356A (en) * | 2019-10-22 | 2020-04-10 | 浙江大学 | Nitrogen fixation device and method based on low-temperature jet plasma coupled monatomic catalysis |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN110983356A (en) * | 2019-10-22 | 2020-04-10 | 浙江大学 | Nitrogen fixation device and method based on low-temperature jet plasma coupled monatomic catalysis |
Non-Patent Citations (2)
| Title |
|---|
| A MoS2 nanosheet-reduced graphene oxide hydrid: an efficient electrocatalyst for electrocatalytic N2 reduction to NH3 under ambient conditions;Xianghong li et. al.;《J. Mater. Chem. A》;第7卷;2524-2528 * |
| Design of basal plane active MoS2 through one- step nitogen and phosphorus co-doping as an efficient pH-universal electrocatalyst for hydrogen evolution;Kaian sun et. al.;《Nano energy》;第52卷;862-869 * |
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